TH2010 Campbell Paul

N° d’ordre 212-2010 Année 2010
THESE
Présentée
devant l’UNIVERSITE CLAUDE BERNARD - LYON 1

ECOLE DOCTORALE DE CHIMIE
SPECIALITE CHIMIE
Pour l’obtention
du DIPLOME DE DOCTORAT
(arrêté du 7 août 2006)
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par
PAUL CAMPBELL
UTILISING THE SOLVATION PROPERTIES OF IONIC LIQUIDS IN THE

SIZE-CONTROLLED SYNTHESIS AND STABILISATION OF METAL
NANOPARTICLES FOR CATALYSIS IN SITU
Directeurs de thèse :
Mme. Catherine SANTINI & M. Yves CHAUVIN
présentée et soutenue publiquement le jeudi 28 octobre 2010 devant la commission d’examen :
Jury: Rapporteurs:
Mme. Anja-Verena MUDRING M. Christopher HARDACRE
M. Agilio PADUA M. Laurent DOUCE
M. Stéphane DANIELE
M. Bruno CHAUDRET (Président)
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2
UNIVERSITE CLAUDE BERNARD - LYON 1
Président de l’Université M. le Professeur L. Collet
Vice-président du Conseil Scientifique M. le Professeur J-F. Mornex
Vice-président du Conseil d’Administration M. le Professeur G. Annat
Vice-président du Conseil des Etudes et de la Vie Universitaire M. le Professeur D. Simon
Secrétaire Général M. G. Gay
COMPOSANTES SANTE
Faculté de Médecine Lyon Est – Claude Bernard Directeur : M. le Professeur J. Etienne

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Faculté de Médecine Lyon Sud – Charles Mérieux Directeur : M. le Professeur F-N. Gilly
UFR d’Odontologie Directeur : M. le Professeur D. Bourgeois
Institut des Sciences Pharmaceutiques et Biologiques Directeur : M. le Professeur F. Locher
Institut des Sciences et Techniques de Réadaptation Directeur : M. le Professeur Y. Matillon
Département de Biologie Humaine Directeur : M. le Professeur P. Farge
COMPOSANTES ET DEPARTEMENTS DE SCIENCES ET TECHNOLOGIE
Faculté des Sciences et Technologies Directeur : M. le Professeur F. Gieres

Département Biologie Directeur : M. le Professeur C. Gautier
Département Chimie Biochimie Directeur : Mme le Professeur H. Parrot
Département GEP Directeur : M. N. Siauve
Département Informatique Directeur : M. le Professeur S. Akkouche
Département Mathématiques Directeur : M. le Professeur A. Goldman
Département Mécanique Directeur : M. le Professeur H. Ben Hadid
Département Physique Directeur : Mme S. Fleck
Département Sciences de la Terre Directeur : M. le Professeur P. Hantzpergue
UFR Sciences et Techniques des Activités Physiques et Sportives Directeur : M. C. Collignon
Observatoire de Lyon Directeur : M. B. Guiderdoni
Ecole Polytechnique Universitaire de Lyon 1 Directeur : M. le Professeur J. Lieto
Institut Universitaire de Technologie de Lyon 1 Directeur : M. le Professeur C. Coulet
Institut de Science Financière et d'Assurance Directeur : M. le Professeur J-C. Augros
3
Institut Universitaire de Formation des Maîtres Directeur : M R. Bernard
for my brothers and sisters; Sandra, Steven, Ian and Beth
and for my Mum and Dad

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4
Les travaux exposés dans ce mémoire ont été réalisés entre novembre 2007 et octobre
2010 au Laboratoire de Chimie, Catalyse, Polymérisation et Procédés dans l’équipe de Chimie
OrganoMétallique de Surface, unité mixte CNRS-CPE Lyon. Je suis reconnaissant envers
Monsieur Gérard Pignault, directeur de CPE Lyon, pour m’avoir accueilli dans ses locaux.
Mes remerciements vont tout d’abord à Madame Bernadette Charleux, qui a bien voulu
m’accueillir au sein de son laboratoire et Monsieur Jean-Marie Basset, qui m’a
chaleureusement accueilli au sein de son équipe.
J’adresse mes plus vifs remerciements à Monsieur Yves Chauvin, Directeur de Recherche
honoraire à l’Institut Français du Pétrole, agissant en qualité de co-directeur. En dépit de son
éloignement, il a fait preuve d’une grande disponibilité et a été une source constante de conseils
et de réflexions. Je lui suis très reconnaissant de sa contribution au développement de ce projet
et de m’avoir fait profiter de ses connaissances et de sa grande expérience en chimie.
Je tiens à remercier Madame Catherine Santini, Directeur de Recherche au CNRS, qui a
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encadré mes travaux de thèse. Je la remercie tout particulièrement pour l’aide et le soutien
qu’elle m’a apportés durant ces trois années.
Que Madame Anja-Verena Mudring, Professeur à la Ruhr Universität Bochum, et
Messieurs Christopher Hardacre, Directeur de l’école de chimie à la Queen’s University Belfast,
Laurent Douce, Directeur de Recherche au CNRS, Agílio Pádua, Professeur à l’Université
Blaise Pascale Clermont Ferrand, Bruno Chaudret, Directeur de Recherche au CNRS et
Stéphane Daniele, Professeur à l’Université Lyon 1, soient vivement remerciés de l’honneur
qu’ils m’ont fait en acceptant de juger ce mémoire.
Ce travail a été finance par la Ministère de l’enseignement supérieur et de la recherche
et par l’Agence Nationale de la Recherche, projet CALIST (ANR-07-CP2D-02-03). Je remercie
tout particulièrement Ajda Podgoršek, Gorka Salas, Margarida Costa Gomes et Karine
Philippot, collaborateurs sur ce projet, pour l'aide et les nouvelles idées qu'ils m'ont apportés. Je
tiens également à remercier Anne Baudouin, François Bayard, Bernard Fenet, Denis Bouchu,
Vincent Collière, et Jacinto Sá pour leurs analyses et leur aide.
Je souhaite également remercier tous les étudiants en stage avec lesquels j’ai eu le grand
plaisir de travailler. Je remercie particulièrement Georgina Fraser et Magali Pillot, étudiantes
en stage de Master, qui ont contribué de façon significative à l’aboutissement de ces travaux.
Que tous les membres du laboratoire trouvent dans ces quelques lignes l’expression de
ma plus profonde gratitude. Je pense en particulier à Jeff, Etienne, Marco, Raphael, Nicolas,
Layane et Vickie avec lesquels j’ai vécu ces trois années dans une ambiance qui fut toujours
conviviale.
5
The work presented in this thesis was carried out between November 2007 and October
2010 in the “Laboratoire de Chimie, Catalyse, Polymères et Procédés” in the team “Chimie
OrganoMétallique de Surface”, CNRS-CPE Lyon. I am grateful Gérard Pignault, director of
CPE Lyon, for welcoming me in his institution.
My warm thanks go firstly to Bernadette Charleux, for welcoming me into her laboratory
and to Jean-Marie Basset, for his willingness to accept me as part of his team.
I am indebted to Mr. Yves Chauvin, honorary research director at the “Institut Français
du Pétrole,” acting as my co-supervisor. Despite his distance, he was always available and has
been a constant source of thought and advice. I am grateful to him for his contribution in the
development of this project and for giving me the opportunity to learn from his great knowledge
and experience in chemistry.
It is difficult to overstate my gratitude towards my Ph.D. supervisor, Catherine Santini,
CNRS Research Director, without whom, this thesis would not have been possible. With her
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enthusiasm, her inspiration, and her great efforts to encourage and give sound ideas and advice,
these three years have been made tremendously enjoyable.
I also extend my sincere gratitude to Anja-Verena Mudring, Professor at Ruhr
Universität Bochum, Christopher Hardacre, Head of the School of Chemistry, Queen’s
University Belfast, Laurent Douce, CNRS Research Director, Agílio Pádua, Professor at
Université Blaise Pascale Clermont Ferrand, Bruno Chaudret, CNRS Research Director and
Stéphane Daniele, Professor at Université Lyon 1, for doing me the honour of reviewing this
thesis.
This work was funded by the “Ministère de l’enseignement supérieur et de la recherché”
and by the “Agence Nationale de la Recherche” under the project CALIST (ANR-07-CP2D-02-
03). I would particularly like to thank Ajda Podgoršek, Gorka Salas, Margarida Costa Gomes
and Karine Philippot, collaborators on this project, for the help and ideas and fruitful discussion
that they provided. I also wish to thank Anne Baudouin, François Bayard, Bernard Fenet, Denis
Bouchu, Vincent Collière, and Jacinto Sá for their analyses and help in interpretation.
It has been a great pleasure to work alongside many undergraduate students during these
three years and I would especially like to give a mention to Georgina Fraser and Magali Pillot,
Master’s students, who both made significant contributions to the outcome of this work.
Last but not least, I would like to express my deepest gratitude to my many colleagues for
providing a stimulating and fun environment in which to learn and grow. I am above all grateful
to Jeff, Etienne, Marco, Raphael, Nicolas, Layane and Vickie for all the emotional support,
camaraderie and particularly for the entertainment that they provided.
6
Abbreviations and acronyms
Units
h: hour min: minute mL: millilitre
g: gram mg: milligram mol: mole
°C: degree Celsius Hz: Hertz K: degree Kelvin
ppm: part per million
Techniques
ESI: ElectroSpray Ionisation Mass Spectrometry
GC: Gas Chromatography
FID: Flame Ionisation Detector
SAXS: Small Angle X-ray Scattering
XRD: X-Ray diffraction
XPS: X-ray photoelectron spectroscopy
NMR: Nuclear Magnetic Resonance
į: chemical shift J: coupling constant
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s: singlet, d: doublet, t: triplet, q: quadruplet, quint: quintuplet, sext: sextuplet, m: multiplet

ROESY: Rotational Overhauser Effect SpectroscopY
DOSY: Diffusion Order SpectroscopY
TEM: transition electron microscopy HREM: high resolution electron microscopy
Chemicals
IL: Ionic Liquid
Im: imidazolium
C1: methyl C2: ethyl C4: butyl C6: hexyl C8: octyl C10: decyl
C4//: but-3-enyl Bz: benzyl
[C1C4Im]: 1-butyl-3-methylimidazolium [C1C1C4Im]: 1-butyl-2,3-dimethylimidazolium
[OTf]: trifluoromethylsulfonate [NTf2]: bis-(trifluoromethylsulphonyl)imide
[BF4]: tetrafluoroborate
COD: 1,5-cyclooctadiene COT: 1,3,5-cyclooctatriene COA: cyclooctane

To: toluene
CYD: 1,3-cyclohexadiene CYE: cyclohexene CYA: Cyclohexane
Lim: (R)-(+)-limonene
Sty: styrene EBn: Ethylbenzene ECHA: ethylcyclohexane
Ru(COD)(COT): (1,5-cycooctadiene)(1,3,5-cyclooctatriene)ruthenium
Ni(COD)2: bis(1,-5(-cyclooctadiene)nickel
NP: nanoparticle
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Abstract – Résumé
UTILISING THE SOLVATION PROPERTIES OF IONIC LIQUIDS IN THE SIZE-

CONTROLLED SYNTHESIS AND STABILISATION OF METAL NANOPARTICLES FOR
CATALYSIS IN SITU
Imidazolium based ionic liquids (ILs) consist of a continuous 3-D network of ionic channels,
coexisting with non polar domains created by the grouping of lipophilic alkyl chains, forming dispersed
or continuous microphases. The aim of this work is to use the specific solvation properties of ILs, related
to this 3-D organisation, to generate and stabilise in situ metal nanoparticles (NPs) of a controlled and
predictable size. This approach has found application in fields such as catalysis and microelectronics. The
phenomenon of crystal growth of NPs (ruthenium, nickel, tantalum) generated in situ in ILs from the
decomposition of organometallic complexes under molecular hydrogen, is found not only to be controlled
by i) the size of non-polar domains, in which the complexes dissolve, but also by ii) the experimental
conditions (temperature, stirring) and iii) the nature of the metal and its precursor complex. The
previously unexplained stabilisation mechanism of NPs in ILs is found to depend on the mechanism of
formation of NPs, which may lead to the presence of either hydrides or N-heterocyclic carbenes (NHC) at
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their surface. These have both been evidenced through isotopic labelling experiments analysed by NMR
and mass spectrometry. Another advantage of ILs is that they provide an interesting medium for catalytic
reactions. Studies on the influence of the IL on the catalytic performance in homogeneous catalysis have
highlighted the crucial importance of the physical-chemical parameters of ILs, in particular the viscosity,
for which a term must be included in the kinetic rate law. Using these findings, a thorough investigation
of the effect of the NP size on catalytic activity and selectivity in hydrogenation in ILs was undertaken,
confirming the importance of controlling NP size for catalytic applications.
UTILISATION DES PROPRIETES DE SOLVATATION DES LIQUIDES IONIQUES EN

SYNTHESE ET STABILISATION DES NANOPARTICULES METALLIQUES DE TAILLE
CONTROLEE POUR LA CATALYSE IN SITU
Les liquides ioniques (LIs) à base d’imidazolium présentent une très grande organisation en
réseaux 3D et sont constitués de microdomaines polaires et apolaires, dû à la présence des canaux
ioniques et le regroupement des chaînes alkyles lipophiles. L’objectif de ce travail est d’utiliser leurs
propriétés de solvatation, liées à cette organisation, pour générer et stabiliser in situ des nanoparticules
métalliques (NPs) d’une taille contrôlée et prévisible. Cette approche a trouvé de nombreuses applications
dans des domaines tels que la catalyse et la microélectronique. Le phénomène de croissance cristalline des
NPs (ruthénium, nickel et tantale) générées in situ lors de la décomposition sous H2 des complexes
organométalliques, est contrôlé i) par la taille des poches apolaires, dans lesquelles le complexe se
dissout, ii) par les conditions expérimentales (température, agitation) et iii) par la nature du métal et du
complexe précurseur. Le mécanisme de stabilisation des NPs, jusqu'alors mal compris, dépend du
mécanisme de formation des NPs, qui pourrait entraîner la présence de ligands hydrures ou carbènes N-
hétérocycliques (NHC) à leur surface. Cette présence a été démontrée par marquage isotopique et
analysée en RMN ainsi qu’en spectrométrie de masse. Les LIs sont également des milieux intéressants en
catalyse. Des études sur l’influence du LI sur l’activité des catalyseurs homogènes ont souligné
l’importance cruciale des paramètres physico-chimiques des LIs, et particulièrement de la viscosité, qui
intervient ainsi dans la loi cinétique. Enfin, une étude approfondie de l’effet de la taille des NPs sur
l’activité catalytique et la sélectivité pour l’hydrogénation, réalisée en milieu LI, a confirmé l’importance
du contrôle de la taille des NPs pour les applications catalytiques.
9
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10
Table of Contents
Table of Contents
Introduction 13
Chapter 1 Ruthenium Nanoparticles 19

Synthesis, Stabilisation & Applications
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Chapter 2 Generation and Stabilisation of Transition Metal 51

Nanoparticles in Imidazolium Ionic Liquids
Chapter 3 Imidazolium Ionic Liquids as Media for Homogeneous 105

Catalysis
Chapter 4 Nanoparticle Catalysis in Imidazolium Ionic Liquids 155

The influence of size on catalytic performance
General Conclusion 187
Appendix 1 Characterisation of Nickel Nanoparticles by XPS 195
Appendix 2 Publications 199
Appendix 3 Separation of Hafnium from Zirconium in Ionic Liquids 235
11
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12
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Introduction
13
Intro
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14
Introduction
Introduction
Progress in the comprehension of metallic nanoparticles (NPs) is central due to their great
potential in the development of new and innovative materials for applications in areas such as
catalysis or microelectronics. Their small sizes, generally reported between 1 and 100 nm, lead
to unique physical-chemical properties between the bulk and molecular states, which vary
greatly with small changes in NP size. For example, the catalytic properties of NPs are largely
determined by the energy of the surface atoms, in turn controlled by the number of neighbouring
atoms, dictated by their size, as well as the presence and nature of ligands or supports.1-3
Particles less than 10 nm in diameter are particularly interesting in catalysis, due to their
high surface to volume ratio, and are also greatly influenced by the aforementioned size-effect.
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Their preparation by most traditional methods often yields catalysts with broad size distributions.
More recent advances in the field have seen the synthesis of NPs with well controlled size
(narrow distribution), shapes and composition.4-6
NPs are only kinetically stable, the thermodynamically stable state being the bulk metal.
Consequently, NPs dissolved freely in solution tend to agglomerate and coalesce. To prevent
aggregation, NPs must be stabilised by the use of stabilising agents such as water-soluble
polymers, quaternary ammonium salts, surfactants or polyoxoanions, providing electronic and/or
steric protection.4-6
In this context, ionic liquids (ILs), defined as low temperature molten salts, have emerged
as one of the most important and most investigated classes of stabilising agent for the synthesis
and stabilisation of metal NPs. My Ph.D. thesis focuses on the overlap of these two prevailing
fields of research, studying the synthesis small size controlled NPs (< 5 nm) for use in catalysis
in situ in ILs.7
We can tune the IL moieties and reaction conditions to obtain monodisperse and
catalytically active NPs of controlled size.4, 7-9 This is because imidazolium based ILs exhibit a
3-D organisation in the liquid state due to an extended hydrogen-bond network of ionic channels,
coexisting with non-polar domains created by the grouping of lipophilic alkyl chains.
Consequently, ILs present specific solvation properties.10 Polar substrates are preferentially
dissolved in polar domains and non-polar compounds in non-polar ones.11 The non-polar
organometallic complex, Ru(COD)(COT), is expected to be concentrated in the non-polar
15
Introduction
domains of ILs. Therefore the phenomenon of crystal growth is controlled by the local
concentration of Ru(COD)(COT) and consequently limited to the size of the non-polar domains.
These play the role of nanoreactors in which the size of ruthenium nanoparticles generated in situ
can be controlled.9, 12, 13 As a result, ILs may be used for predictive size-control of RuNPs.
Another major advantage of using ILs is that stabilising additives such as ligands,
polymers and supports are not required, meaning that a maximum amount of NP surface is
available for the coordination of substrates. However, the reasons behind the stability of NPs
dispersed in ILs remain under debate.14
After a brief literature survey of the synthesis and catalytic applications of RuNPs in
various media (Chapter 1), we go on to investigate the exact stabilisation mechanism of RuNP/IL
solutions (Chapter 2). Also, we attempt to generalise the size-controlled NP synthesis of
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transition metal nanoparticles, by investigating the synthesis of nickel and tantalum NPs in the
same media (Chapter 2).
In order to study the catalytic reactivity in ionic liquids, we must have an understanding
of how the physical-chemical properties of these media themselves may influence the outcome
of a given reaction. For this reason, we carry out a kinetic study of a simple homogeneous
hydrogenation reaction (1,3-cyclohexadiene over an Osborn-type cationic Rh catalyst) in
different IL media, simultaneously probing the thermophysical properties (viscosity, density,
diffusion) and intermolecular interactions of the IL-substrate mixtures. These findings are used
to rationalise the differences in reactivity and thus gauge the important parameters to consider
when carrying out catalysis in IL media. (Chapter 3)
Finally, using the IL media to synthesise tailor-made RuNPs of distinct sizes, we may
investigate the size-effect on catalytic performance (activity, selectivity) in the hydrogenation of
several substrates including 1,3-cyclohexadiene, taking into account our findings from Chapter 3
to ensure otherwise identical reaction conditions. (Chapter 4)
16
Introduction
References
1. M. Valden, X. Lai and D. W. Goodman, Science, 1998, 281, 1647.
2. A. T. Bell, Science, 2003, 299, 1688 –1691.
3. G. Schmid, Nanoparticles: From Theory to Application, Wiley-VCH, Weinheim, 2004.
4. H. Boennemann, K. S. Nagabhushana and in Metal Nanoclusters in Catalysis and
Materials Science: The Issue of Size Control ed. B. Corain, Schmid, G., Toshima, N.,
Elsevier B.V, Amsterdam, 2008, pp. 21-48.
5. D. Astruc, Nanoparticles and Catalysis, Wiley-VCH, Weinheim, 2008.
6. D. Astruc, F. Lu and J. R. Aranzaes, Angew. Chem. Int. Ed., 2005, 44, 7852.
7. J. Dupont and J. D. Scholten, Chem. Soc. Rev., 2010, 39, 1780-1804.
8. J. Dupont, in Nanoparticles and catalysis, Wiley-VCH, Weinheim, 2008.
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9. T. Gutel, C. C. Santini, K. Philippot, A. Padua, K. Pelzer, B. Chaudret, Y. Chauvin and

J.-M. Basset, J. Mater. Chem., 2009, 19, 3624-3631.
10. A. A. H. Padua, M. F. Costa Gomes and J. N. A. Canongia Lopes, Acc. Chem. Res., 2007,
40, 1087-1096.
11. J. N. Canongia Lopes, M. F. Costa Gomes and A. A. H. Padua, J. Phys. Chem. B, 2006,
110, 16816-16818.
12. T. Gutel, J. Garcia-Anton, K. Pelzer, K. Philippot, C. C. Santini, Y. Chauvin, B. Chaudret
and J.-M. Basset, J. Mat. Chem., 2007, 17, 3290-3292.
13. P. S. Campbell, C. C. Santini, D. Bouchu, B. Fenet, K. Philippot, B. Chaudret, A. A. H.
Padua and Y. Chauvin, Phys. Chem. Chem. Phys. 2010, 12, 4217-4223.
14. R. G. Finke, Coord. Chem. Rev., 2007, 251, 1075–1100.
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18
I
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Chapter 1
Ruthenium Nanoparticles
Synthesis, Stabilisation &

Applications
19
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20
Chapter 1 Ruthenium Nanoparticles – Synthesis, Stabilisation and Applications
Chapter 1
Ruthenium Nanoparticles
Synthesis, Stabilisation and Applications
1.1 Introduction .................................................................................................................................... 23
1.2 Syntheses ....................................................................................................................................... 24
1.2.1 RuNPs synthesised directly on supports .................................................................................... 24

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1.2.2 Solvothermal synthesis .............................................................................................................. 25
1.2.3 Colloidal synthesis in organic solvents...................................................................................... 27
1.2.4 Aqueous Synthesis..................................................................................................................... 31
1.2.5 Synthesis in ionic liquids ........................................................................................................... 32
1.2.6 Glossary of RuNP syntheses...................................................................................................... 34
1.3 Catalytic properties ........................................................................................................................ 36
1.3.1 Nitrogen activation .................................................................................................................... 36
1.3.2 Surface hydrides on RuNPs ....................................................................................................... 37
1.3.3 Arene hydrogenation ................................................................................................................. 37
1.3.4 C=O hydrogenation ................................................................................................................... 38
1.3.5 NO2 hydrogenation .................................................................................................................... 39
1.3.6 Asymmetric hydrogenation ....................................................................................................... 39
1.3.7 Oxidation ................................................................................................................................... 41
1.3.8 Miscellaneous ............................................................................................................................ 42
1.3.8.1 Cellubiose hydrolysis ........................................................................................................ 42
1.3.8.2 Hydrogen Generation ........................................................................................................ 43
21
1.3.8.3 Synthesis of novel functional materials ............................................................................ 43
1.4 Conclusion ..................................................................................................................................... 44
1.5 References ...................................................................................................................................... 45

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22
1.1 Introduction
Interest in metal nanoparticles (NPs) is increasing dramatically, as reflected by the ever-

growing number of publications. Catalysis is the traditional application of NPs, but they also find
application in diverse fields such as photochemistry, electronics, optics or magnetism. In
catalysis, progress is constantly being made in the efficiency and selectivity of reactions and
recovery and recyclability of the catalytic materials.1-8
Usually NP catalysts are prepared from a metal salt, a reducing agent, and a stabiliser and
are often supported on an oxide, charcoal, or a zeolite. However, soluble noble metal
nanoparticles are also to be considered as an unavoidable family of catalysts, often described as
“semi-heterogeneous catalysts”, lying at the frontier between homogeneous and heterogeneous
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chemistry. Besides the polymers and oxides that used to be employed as standard, innovative
stabilisers, media, and supports have appeared, such as dendrimers, specific ligands, ionic
liquids, surfactants, membranes, carbon nanotubes, and a variety of oxides.9-14
As one of the catalytically active noble metals, ruthenium has been widely studied in both
homogeneous catalysis, the most well known example being olefin metathesis,15, 16 and in
heterogeneous, for example the partial hydrogenation of benzene to cyclohexene (Asahi
process),17 phenol hydrogenation,18 or in the synthesis of ammonia from N2 (Haber-Bosch
process).19, 20
Over the past couple of decades, much interest has also been devoted towards
nanoparticles of ruthenium, even though it is claimed by Galetti et al. that the preparation of Ru
nanoparticles is more difficult and therefore less-investigated than other noble metals such as Pt
or Pd.18 Their various synthetic routes and catalytic properties are summarised in this chapter.
23
1.2 Syntheses
1.2.1 RuNPs synthesised directly on supports

The study of RuNPs and their use in catalysis is not a new concept and dates back to the
1980s. Grafting of catalytically active metal complexes onto oxide supports, a technique
commonly referred to as surface organometallic chemistry, was becoming a popular area of
interest due to the prospect of combining the advantages of heterogeneous and homogeneous
catalysis (i.e. obtaining recoverable, reusable catalysts with high activity and selectivity), as well
as obtaining new and novel catalysts.21 This method involves firstly impregnation of the support
with a solution (aqueous or organic) of metal precursor, followed by elimination of the solvent
and finally thermal treatment, generally under H2 or vacuum. However, for late transition metals
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such as ruthenium, after thermal treatment, these surface complexes, e.g. Ru3(CO)12, tend to
decompose and agglomerate, forming small oxide-supported RuNPs (1-2 nm on SiO2, measured
by TEM).22-25 Nonetheless, these supported NPs have been found to display interesting catalytic
behaviour, for example in the hydrogenolysis and homologation of olefins.26, 27
The use of the organometallic precursor ruthenium(η4-1,5-cyclooctadiene)(η6-1,3,5-
cyclooctatriene), commonly denoted Ru(COD)(COT), for the formation of RuNPs supported on
SiO2 was first reported Kitajima et al. This method rendered very small NPs ~ 1 nm, (measured
by H2 adsorption) smaller than those produced from RuCl3 via the same method.28 This is
thought to be due to the absence of coordinating Cl-, which would be present in the latter case.
Bare RuNPs prepared in this way have been found to coordinate 2 hydride ligands per surface
site.29
Similarly, RuNPs have been supported on mesoporous silica, firstly by impregnating the
support with Ru(COD)(COT) solution in THF and then proceeding to decompose the complex.
The size of the NPs obtained varies with the pore size and the impregnation method.30
Alumina supports (Al2O3) have also been studied and give similar results. For example,
impregnation of a precursor (either RuCl3 or Ru3(CO)12) on a K-promoted alumina (added by
prior impregnation of the alumina with KOH) followed by reduction at 400 °C under a flow of
H2 produced supported RuNP catalysts. The size distribution and dispersion were found to be
superior in the case where Ru3(CO)12 was used as the precursor.31
24
This technique has also been extended to innovative supports such as mesoporous
polymers to create new catalytic materials as depicted in Scheme 1. This can be used as a highly
recyclable catalyst in the aqueous hydrogenation of olefins and aromatics.32
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Scheme 1. The synthesis of a RuNP-loaded mesopolymer for catalysis. 32
Although the direct synthesis of supported NPs in this fashion renders catalytically active
supports, due to the absence of ligands and availability of the NP surface, the resulting size and
size distribution, a factor which dictates catalytic performance, is difficult to control. For this
reason the deposition of ready-synthesised RuNPs onto supports has also received a great deal of
interest.
1.2.2 Solvothermal synthesis
The versatile and facile polyol method for the synthesis of nanoparticles involves firstly
suspending the metal precursor in a polyol such as ethylene glycol, before bringing the resulting
mixture to reflux and awaiting the precipitation of the metallic moieties. The reduction occurs
via the simultaneous oxidation of alcohols to aldehydes as shown in Equation (1). The resulting
metal NPs can be filtered and dried in air. Using RuCl3 as the metal precursor results in RuNPs
with an average diameter of 5 nm.33
3 –CH2OH (from polyols) + RuCl3 à 3 -CHO + 2 Ru(0) + 6 HCl (1)
25
The polyol method has been used in the presence of polyvinylpyrrolidone (PVP) to
obtain polymer-supported RuNPs by microwave-assisted syntheses.34-36 The size of the resulting
RuNPs may be controlled by the concentration of the precursor, as shown by Somorjai’s group
using Ru(acac)2 (acac = acetylacetonate) in a microwave-assisted synthesis. TEM images of the
size-controlled RuNPs produced are depicted in Figure 1. The PVP-stabilised RuNPs could then
be supported on silicon wafers for gas phase catalysis.37
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Figure 1. TEM images of Ru NPs: (a) 2.1, (b) 2.8, (c) 3.1, (d) 3.8, (e) 5.0, and (f) 6.0 nm. TEM images were taken
using a Philips FEI Tecnai 12 machine, operated at 100 kV. 37
RuNPs produced via the polyol method, subsequently coated in dodecane thiol and
dispersed in toluene, have been found to form supramolecular self-assemblies of anisotropic
disc-shaped NPs, the structure varying with the thiol concentration, Figure 2.
26
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Figure 2. Supramolecular self assemblies of hexagonal RuNP prepared via the polyol method and stabilised with
dodecane thiol.38
This method has been widely used for subsequent deposition of the NPs onto oxide
supports. For example Miyakazi et al. prepared RuNPs supported on γ-alumina via the polyol
method for use in heterogeneous catalysis. It was found that the best results for size-control were
obtained when the γ-alumina was present during the polyol reduction, as this prevented NP
agglomeration during the cooling of the polyol mixture. The RuNPs are supported on the
alumina by electrostatic forces.20 Similarly, Xu et al. used the polyol method in ethylene glycol
to stabilise RuNPs produced in situ onto MgO substrates.39
Similar to the polyol route, another solvothermal route has been used to produce RuNPs
directly from RuCl3 by heating with an anhydrous alchohol, such as methanol. Upon heating
Ru(III) may oxidise the methanol to formaldehyde, reduced itself to Ru(0) as shown in Equation
(1).40 The RuNPs produced using this method were found to be between 2 and 10 nm in size and
X-ray diffraction analysis indicated the presence of a Ru hcp phase. XPS experiments, however,
indicated a slightly oxidised surface, possibly due to coordination of residual chloride.40
1.2.3 Colloidal synthesis in organic solvents
Zero-valent organometallic precursors are generally easily decomposed under H2
atmosphere rapidly producing NPs. The organic by-products can be easily removed without
further interaction with the surface of the resulting NPs. For this reason, Chaudret’s group has
27
thoroughly developed the synthesis of RuNPs in organic solvents from the decomposition of the
organometallic precursor Ru(COD)(COT), Scheme 2.12, 41-43
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Scheme 2. The synthesis of RuNPs from the decomposition of Ru(COD)(COT) in organic solvents.12
In mixtures of methanol/THF of varying composition, this decomposition may take place

resulting in RuNPs of sizes varying linearly with MeOH/THF ratio, Figure 3a.44, 45 These
surprising results have been attributed to a colloidal growth mechanism involving micellar type
aggregates of MeOH and cyclooctane (resulting from hydrogenation of the ruthenium precursor)
acting as nanoreactors in which the size of the RuNPs is constrained, Scheme 3.
Scheme 3. Hypothesised growth and stabilisation mechanism for RuNPs in THF methanol mixtures.43
In a mixture of MeOH/THF 10:90, the size of NPs generated was found to vary inversely
with the temperature used during decomposition, Figure 3b. This could be explained by
28
considering the effect of the temperature on the kinetics of decomposition. At higher T, the
decomposition is accelerated and therefore nucleation is rapid leading to a large number of small
particles. At low temperature, decomposition is slow and the kinetics of coalescence dominate.46
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Figure 3. a) variation of RuNP size with MeOH composition (left), b) variation of RuNP size with decomposition
temperature (right).44-46
Through tests of their reactivity towards O2 and CO, the resulting NPs are shown to be
“bare” and therefore have a great surface availability for catalysis. Furthermore, RuNPs
produced in such a manner have been supported on porous alumina membranes, Figure 4, and
used in the gas phase hydrogenation of butadiene.44
Figure 4. RuNPs produced in MeOH/THF mixtures from the decomposition under H 2 of Ru(COD)(COT),
supported in a porous alumina membrane.44
This synthesis has also been carried out in the presence of polymeric materials. For
example with nitrocellulose in THF, polymer-supported NPs were produced. Here, varying the
29
ratio of Ru/nitrocellulose was found to control the size of the resulting NPs (2 % - 1.5 nm, 10 % -
2.5 nm).47
In the presence of the polymers polyvinylpyrrolidone (PVP) or cellulose acetate (CAC),
polymer supported RuNPs of 1.1 nm or 1.7 nm result. High resolution electron microscopy
(HREM) images show that these NPs adopt a relaxed hcp structure – a = 2.66 Å, c = 4.36 Å
compared to a = 2.7058 Å and c = 4.2811 Å in bulk ruthenium, Figure 5.48
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Figure 5. HREM image of RuNPs produced inTHF in the presence of PVP.48
Colloidal solutions of RuNPs may also be prepared by using ligands such as amines in
THF. Varying the length of the alkyl chain of the amines used, as well as the quantity of amine
has been found to produce RuNPs of different sizes and shapes. Elongated RuNPs produced
using 0.5 equivalents of hexadecylamine with respect to ruthenium are shown in Figure 6.48
RuNPs prepared in THF and stabilised with hexadecylamine have been proven by H-D exchange
experiments to be covered by surface hydrides, which may provide an additional explanation for
their stability.49
Figure 6. Elongated RuNPs formed in a mixture of THF and hexadecylamine (0.5 equiv.) 48
30
A range of thiols has also been studied as potential ligands for the stabilisation of RuNPs
in organic solvent. However, agglomeration was noted in this case, possibly related to the
dimerisation of thiols to disulphides on the RuNP surface, Equation (2), observed by NMR
spectroscopy.48
(2)
Silanes may also be used to stabilise RuNPs in organic solvent. The grafting of the silane
to the NP surface has been observed by solid state NMR spectroscopy.50
From an environmentally-friendly point of view, aqueous catalytic processes are a highly
interesting concept. Indeed, it has been found that the careful selection of a hydrophilic
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stabilising ligand in NP synthesis leads to RuNPs which may be redispersed in water for
catalysis.51, 52 An example depicted in Scheme 4 uses 1,3,5-triaza-7-phosphaadamantane, PTA to
stabilise water soluble RuNPs.51
Scheme 4. The synthesis of water soluble RuNPs in THF.
Of course, synthesis of water-soluble RuNPs may also take place in situ starting from
aqueous solutions of water soluble Ru precursors.
1.2.4 Aqueous Synthesis
For synthesis of NPs in water, non-polar organometallic precursors such as
Ru(COD)(COT) are no longer suitable. Instead, metal salts are used, in the case of RuNPs,
RuCl3.
Roucoux’s group has undertaken much work on the aqueous synthesis of RuNPs from
reduction of RuCl3 with NaBH4 in the presence of cyclodextrins (Scheme 5), which stabilise the
31
resulting NPs by formation of inclusion complexes. The cyclodextrins, which are water-soluble,
may also modify the surface of the RuNPs for specific reactivity.53-55
Scheme 5. Schematic representation of α-, β- and γ-cyclodextrins containing 6, 7 and 8 glucopyranose units
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respectively.54
Water-soluble RuNPs have also been achieved using similar experimental conditions but
with less complicated ligands such as ethylenediamine,56, 57 sodium acetate,58 or even polymers
such as poly(4-vinylpyridine).59 These aqueous media may be used in biphasic catalytic systems
for reactions such as hydrogenations, presenting the advantage of easy catalyst recyclability and
product separation.53-55
The possibility of producing RuNPs that can be dispersed in a variety of media by using
amphiphilic ligands has also been explored.60
1.2.5 Synthesis in ionic liquids
Due to their specific solvation properties and 3-D structural organisation in the liquid
state, ionic liquids are “supramolecular fluids” that can be used as ‘‘entropic drivers’’ for the
spontaneous, well-defined and extended ordering of nanoscale structures. This includes the
synthesis of NPs, which can take place with size-control and in the absence of stabilising
additives. The number of publications in this field is increasing exponentially, and these have
recently been comprehensively reviewed.14
RuNPs were first generated “by accident” in ionic liquids. During an investigation of the
catalytic hydrogenation behaviour of RuO2 in ionic liquids, Hg and CS2 poisoning tests
confirmed that the catalytically active species was in fact colloidal Ru(0). The presence of NPs
32
was confirmed by TEM, meaning that under mild hydrogenation conditions, RuO2 was reduced
forming a stable suspension of small NPs in the ILs.61, 62
Organometallic precursors such as bis(2-methylallyl)(η4-1,5-cyclooctadiene)ruthenium63
and Ru(COT)(COD) have also been used as a RuNP precursor in ILs.62 Ru(COD)(COT),
particularly in imidazolium ILs based on the NTf2 ion, renders interesting results.64
Firstly, work undertaken in our laboratory uncovered that, unlike in traditional solvents,46
decreasing the temperature of decomposition to 0 °C (hence decreasing rate of nucleation) leads
to smaller NPs. This could only be explained by considering the organisation of the ionic liquid,
which consists of rigid ionic channels and segregated lipophilic domains. The organometallic
precursor dissolves preferentially within these lipophilic domains. The size of the resulting
RuNP is dictated by the number of available nuclides in the non polar domain after
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decomposition. At low temperature, diffusion of the precursor and nuclides between these
domains is limited, hence the growth of NPs is restricted.
This can be confirmed by observing the effect of stirring on the size distribution. Stirring
disrupts the organisation through mechanical forces and increases the diffusion of the precursor
and nuclides in solution. The resulting size distributions are therefore broader and the resulting
NPs are agglomerated.64
Further control of the size of NPs generated in these ionic liquids can be achieved by
controlling the size of the non-polar domains by altering the length of the alkyl chains.65
Ionic liquids have also been used in combination with supports to synthesise and stabilise
RuNPs of a small size. The ionic liquid 1,1,3,3-tetramethylguanadinium (TMG) lactate has been
used to immobilise NPs in mesoporous silica (SBA-15). The resulting material was found to
exhibit synergistic effects between the RuNPs, the support and the TMG+, resulting in an active
catalyst in arene hydrogenation.66
33
1.2.6 Glossary of RuNP syntheses
Table 1. Non-exhaustive glossary of RuNP syntheses reported in the literature, and sizes obtained.
Precursor Conditions Stabiliser/Solvent Size obtained (nm) Reference
Ru(COD)(COT) 100-400 °C, H2 SiO2 0.9-1.0 (depending on 28
(270 mbar) decomposition temperature
and loading)
RuCl3 1.5-5.3 (depending on
loading)
Ru(COD)(COT) 300 °C, H2 SiO2 2.0 ± 0.3 29
(666 mbar)
Ru3(CO)12 220 °C, H2 (1 bar) SiO2 1 25
Ru3(CO)12 120 °C, vacuum SiO2 1.4 22
RuCl3 400 °C, H2 (1 bar) Al2O3- KOH 10 31
Ru3(CO)12 400 °C, H2 (1 bar) 2
RuCl3 reflux Ethylene glycol 5 20, 33
RuCl3 150 °C, NaOAc 1,3-propanediol 4 38, 67
RuCl3 reflux Methanol 2 - 10 40
Ethanol
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Ru(COD)(COT) 25 °C, H2 (1 bar) Nitrocellulose/THF 1.0, 1.5, 2.0 47

(2, 5, 10 % Ru, resp.)
Ru(COD)(COT) 21 °C, H2 (3 bar) Methanol/THF 12- >500 (depending on 44-46
MeOH/THF composition)
Ru(COD)(COT) -30 °C, H2 (3 bar) Methanol/THF (10/90) 65 46
-10 °C, H2 (3 bar) 53
0 °C, H2 (3 bar) 41
r.t., H2 (3 bar) 21
30 °C, H2 (3 bar) 15
40 °C, H2 (3 bar) 13
80 °C, H2 (3 bar) 5
Ru(COD)(COT) 20 °C, H2 (3 bar) PVPa/THF 1.1 48
CACb/THF 1.7
Ru(COD)(COT) 20 °C, H2 (3 bar) Octylamine/THF 2.3-2.5 48
Dodecylamine/THF 1.8-2.3 (elongated shapes)
Hexadecylamine/THF 1.9-2.6 (elongated shapes)
(all varying with ligand
amount)
Ru(COD)(COT) 20 °C, H2 (3 bar) Octanethiol/THF 2.3-2.5 48
Dodecanethiol/THF ~2
Hexadecanethiol/THF 1-2
(all varying with ligand
amount)
Ru(COD)(COT) 20 °C, H2 (3 bar) Pure heptanol 3 68
Ru(COD)(COT) -80 °C-r.t. H2 Octylsilane/n-pentane 2.3 50
(3 bar)
Ru(COD)(COT) r.t , H2 (3 bar) Mesoporous silica/THF 2-5 (depending on the pore 30
size and impregnation
method)
Ru(COD)(COT) r.t., H2 (3 bar) N donor chiral ligands/ 1.5-2.7 nm (depending on 69
THF ligand)
Ru(COD)(COT) r.t., H2 (3 bar) Heavily fluorinated ~3 nm grouping into super- 70
compounds/ THF structures
Ru(COD)(COT) r.t., H2 (1 bar) 4-(3-phenylpropyl)- 1.3 ± 0.3 71
pyridine/ THF
Ru(COD)(COT) r.t., H2 (3 bar) Diphosphites/THF 1.8-4.0 (depending on nature 72, 73
34
of diphosphite)
Ru(COD)(COT) 45 °C, H2 (1 bar) Polyorganophosphazanes/ 1.55 ± 0.5 74
THF
Ru(COD)(COT) 70 °C, H2 (3 bar) PTAc/THF 1.3 ± 0.2 51
Ru(COD)(COT) 25 °C, H2 (3 bar) 3-APTSd/THF 1.7 ± 0.4 75
RuCl3 r.t., NaBH4 (aq) Dodecylamine/ 4.1 76
THFe
RuCl3 r.t., NaBH4 methylated cyclodextrins/ 1 – 2.5 53-55
H2O
RuCl3 r.t., NaBH4 Methylenediamine/ 2.1 56
H2O
RuCl3 r.t., NaBH4 NaAcO/ 2.2 ± 1.0 58, 77
H2O
RuCl3 r.t., NaBH4 Poly(4-vinylpyridine)/ 1-2 59
H2O
Ru(COD)(COT) 75 °C, H2 (4 bar) C1C4Im BF4 2.6 ± 0:4 (in 57 nm 62
C1C4Im PF6 superstructures)
C1C4Im OTf
Ru(COD)(COT) 0 °C, H2 (4 bar) C1C4Im NTf2 0.9 ± 0.4 (agglomerated in 2- 64
stirred 3 nm clusters )
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0 °C, H2 (4 bar) C1C4Im NTf2 1.1 ± 0.2

unstirred
25 °C, H2 (4 bar) C1C4Im NTf2 2.4 ± 0.3
stirred
Ru(COD)(COT) 0 °C, H2 (4 bar) C1C2Im NTf2 2.3 ± 0.6 65
unstirred C1C4Im NTf2 1.1 ± 0.2
C1C6Im NTf2 1.9 ± 0.6
C1C8Im NTf2 2.3 ± 0.8
C1C10Im NTf2 100-150 sponges
C1C1C4Im NTf2 1.8 ± 0.5
C4C4Im NTf2 2.0 ± 0.6
Ru(COD)(2-methylallyl)2 50 °C, H2 (4 bar) C1C4Im NTf2 2.1 ± 0.5 63
C1C4Im BF4 2.9 ± 0.5
C1C10Im NTf2 2.7 ± 0.5
C1C10Im BF4 2.1 ± 0.5 78
C1(C3CN)Im NTf2 2.2 ± 0.5
RuO2 75 °C, H2 (4 bar) C1C4Im PF6 2:5 ± 0:4 61
C1C4Im OTf 2.0 ± 0:4
RuCl3 150 °C, H2 (1 bar) 1,1,3,3,-tetramethyl- 2-5 66
guanadinium lactate /
SBA-15
a
polyvinylpyrrolidone. b cellulose acetate. c1,3,5-triaza-7-phosphaadamantane. d 3-aminopropyltriethoxysilane. e NPs formed in
a biphasic medium, extracted into organic phase.
35
1.3 Catalytic properties
As mentioned previously, the major application for metallic NPs is in catalysis. In this
section will be discussed several literature examples of catalytic studies performed using RuNPs
produced in using different methods.
1.3.1 Nitrogen activation
Nitrogen activation for the synthesis of ammonia is an important catalytic challenge for
which the use of RuNPs is reported in the literature.39, 79 In particular, RuNPs supported on γ-
alumina are active in ammonia synthesis.31 Interestingly, it was observed that those prepared
from the impregnation and reduction of Ru3(CO)12 present a better activity than those from
RuCl3 as shown in Figure 7, despite using the same preparation conditions. This is claimed to be
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due to the greater surface available when produced from Ru3(CO)12, emphasising the importance
of the precursor complex chosen.31 Using the polyol method to produce supported RuNPs
resulted in an even higher activity, possibly due to the weaker interactions between the NPs and
the alumina support.20
Figure 7. Dihydrogen conversion as a function of reaction temperature (N2/H2 = 1:3): (×) equilibrium values; (▲)
4.2% Ru [from Ru3(CO)12, activated under helium up to 673 K]/Al 2O3-KOH (25.4% K); (□) 4.2% Ru [from
Ru3(CO)12, activated under hydrogen up to 673 K]/Al2O3-KOH (25.4% K); (○) 5.5% Ru (from RuC13 activated
31
under hydrogen up to 673 K)/A1203-KOH (25.4% K).
36
1.3.2 Surface hydrides on RuNPs

One particularity of Ru, as with many noble metal surfaces, is the tendency to adsorb
labile hydrides when under H2 atmosphere.80, 81 As in many cases the generation of these metallic
NPs is performed under H2, this layer of surface hydrides is probable. Indeed, their presence has
been already proven through H-D exchange experiments in colloidal82 and supported systems.29
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Scheme 6. Ethylene reactivity on RuNP surfaces.82
The activity of Ru in hydrogenation is well known and has been used to titrate the
number of surface hydrides on RuNPs, both supported,29 and in colloidal solutions.82 Scheme 6
illustrates the reactivity of these Ru-H towards ethylene. As well as hydrogenation to give
ethane, many different alkyl species can be formed on the metal surface through hydrogenolysis
and homologation type processes. Therefore, in order to effectively titrate all surface hydrides, it
is important to quantify both the species evolved under ethylene atmosphere and those evolved
during subsequent heating under H2, to account for the surface alkyl species.
1.3.3 Arene hydrogenation
RuNPs are known to be active catalysts in aromatic hydrogenation, and many studies are
reported in the literature. Indeed, it is now commonly believed that in the hydrogenation of
aromatics, the catalytic species cannot be mono-nuclear, as a metal surface is required in order to
activate the π-conjugated system.83
A study by Su et al. compared the reactivity of RuNPs prepared by thermal reduction and
reduction under hydrogen of RuCl3 on various supports (silica and/or carbon). It was consistently
found that the RuNPs prepared through thermal reduction were more active, despite often
exhibiting larger size distributions. These findings were attributed to the more intensive contact
37
between the Ru and the carbon of the support, inducing enhanced hydrogen spill-over effects.
The nature of the support was found to play a crucial role.84
Supported RuNPs have also been found to be effective in the hydrogenation of N-
heterocycles, but not S–heterocycles, unlike tethered Ru(II) catalysts which catalyse effectively
both reactions.25 When supported on polyorganophophazanes, a recyclable catalyst system for
the hydrogenation of various olefins, carbonyls and aromatics results. The material may be
dissolved in environmentally friendly solvents such as water or alcohols, or used in a
heterogeneous manner.74
Colloidal solutions of RuNPs in organic solvent have also been tested in the
hydrogenation of aromatic substrates such as benzene and quinoline. In the case of benzene, a
conversion of 82 % to cyclohexane was obtained after 14 h at 80 °C under 20 bar H2
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([Sulbstrate]/[Ru] = 500, TON = 311, TOF = 16 h-1).44, 46, 68

RuNPs stabilised by cyclodextrins in water have been found to be active in the
hydrogenation of substituted aromatics such as styrene and allylbenzene under biphasic
conditions with the chemoselectivity controlled by the nature of the cyclodextrin ligand.53
When suspended in ILs, RuNPs provide a recyclable system for the biphasic
hydrogenation of arenes.63 The catalytic reaction can be influenced by the nature of the IL. For
example, RuNPs stabilised in nitrile-functionalised ILs have been observed to be selective
towards the hydrogenation of nitriles but do not hydrogenate arenes.78 Furthermore, due to the
solvation properties of ionic liquids, the possibility of extracting cyclohexene during the
hydrogenation of benzene over RuNPs produced in situ has been explored. Here the solubility
difference of the cyclohexene compared to benzene may be exploited to achieve this.62
1.3.4 C=O hydrogenation
The reduction of aldehydes and ketones to alcohols is very easy and mainly performed
with hydride reagents. Nonetheless, due to environmental and economical considerations,
transition metal compounds are often preferred.6
Liu’s team has reported the hydrogenation of citronellal to citronellol using a Ru/PVP
colloid prepared by reduction with NaBH4. High activity and selectivity for the desired
citronellol product was observed, Scheme 7.85
38
Scheme 7. The hydrogenation of citronellal and the possible products. 85

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RuNPs supported onto polyorganophophazanes in THF have been tested in the

hydrogenation of several carbonyl compounds, e.g. cyclohexanone, ethyl acetoacetate, ethyl
pyruvate, pyruvic acid and actetophenone. All were quantitatively converted to the
corresponding alcohol under mild conditions.74
1.3.5 NO2 hydrogenation
Liu and co-workers have also found PVP-stabilised RuNPs to be chemoselective in the
hydrogenation of chloronitrobenzene to chloroaniline. However, the reaction rate is very
slow.86, 87
1.3.6 Asymmetric hydrogenation
Enantio- and stereoselectivity is often an important issue in organic synthesis and
particularly challenging in NP catalysis. Therefore, attention had been devoted to the use of
chiral N- or P- donor ligands as a potential way to induce enantioselectivity and perform
asymmetric hydrogenations. Although asymmetric induction obtained is modest, it reveals the
influence of the asymmetric ligand coordinated to the surface. The results obtained for the
asymmetric hydrogenation of methylanisoles are depicted in Figure 8.69
39
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Figure 8. The synthesis of RuNPs in THF with chrial N-donor ligand, L*, the TEM image of the NPs produced and
the subsequent performance in the asymmetric hydrogenation of methylanisoles. 69
The same catalyst systems were found to be active in hydrogen transfer between iso-
propanol and acetophenone, Scheme 8. The rate of reaction was found to vary with the nature of
the chiral N-donor ligand, and a moderate enantiomeric excess (10 %) was observed in only few
cases.69
69
Scheme 8. Hydrogen transfer between iso-propanol and acetophenone.
40
In another example in the literature, diphosphite ligands have been successfully used to
stabilise small RuNPs in organic solvent and thus perform diastereoselective hydrogenations of
methylanisole,72, 73 while the use of P(m-C6H4SO3Na)3 in combination with a mixture ionic
liquids and water has been shown to produce a recyclable and enantio-selective system for
hydrogenation.88 Furthermore, trioctylamine-stabilised RuNPs in a mixture of alcohol and water
show a certain stereoselectivity in the hydrogenation of various substituted arenes.89
1.3.7 Oxidation
Catalytic oxidation processes, which are of particular interest in industry, may benefit
from progress in the field of nanoclusters, but only very few examples of oxidation reactions
have been reported in the literature.
One significant result has demonstrated the ability of RuNPs to oxidise cycloalkanes
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selectively to the corresponding ketones, e.g. cyclooctane to cyclooctanone, Scheme 9. This has
been achieved with tert-butylhydroperoxide (tBHP) in a water/cyclooctane mixture, with very
high selectivity.90, 91
Scheme 9. Oxidation of cyclooctane to cyclooctanone over RuNPs using tBHP.90, 91
In another catalytic oxidation, RuNPs grafted onto hydroxyapatite have been found to be
active in the cis-dihydroxylation and oxidative cleavage of alkenes, presenting excellent
recyclability.67
The oxidation of CO to CO2 has been achieved quantitatively using RuNPs supported in a
porous alumina membrane. A slight difference was noted in activity with particle size, smaller
particles being slightly more active.92 However, this may have been related to the porous
material, as when supported on a silicon wafer and stabilised by PVP, the inverse trend in
activity with respect to NP size has been observed in the same reaction by Somorjai’s group,
Figure 9.37 This last example demonstrates the importance of the size of the NPs in catalysis, as
well as how altering the nature of the reaction medium or stabilising support may change entirely
the outcome of the reaction under investigation.
41
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Figure 9. The variation of TOF and activiation energy with RuNP size in the catalytic oxidation of CO, studied by
Somorjai’s group.37
1.3.8 Miscellaneous
1.3.8.1 Cellubiose hydrolysis
Water-dispersed RuNPs have been shown to be active in a one-step hydrolysis of
cellobiose to C6 alcohols, an important reaction in the production of bio-fuels, Scheme 10.93
Scheme 10. The single-step conversion of cellobiose to C6 alcohols using RuNPs.93
42
1.3.8.2 Hydrogen Generation

RuNPs dispersed in water have been found to be active catalysts in the hydrolysis of
NaBH4 to produce H2, Equation (3). This is a safe way of producing H2 due to the non-
flammability of the surrounding environment.77
(3)
Very recently, RuNPs coordinated by silane ligands have been found to be highly active
and reusable as catalysts for the dehydrogenation of dimethylamine–borane, which could be an
interesting prospect in solid hydrogen storage materials.75
1.3.8.3 Synthesis of novel functional materials
RuNPs have been found to be active and efficient catalysts for growth of single-walled
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carbon nanotubes (SWNTs), an increasingly important material in fields such as

microelectronics. This occurs via a chemical vapour deposition (CVD) process.81 RuNPs
dispersed in hybrid nanomaterial are also reported as attractive materials for catalytic filters in
gas sensors.94
43
1.4 Conclusion
As we can see, there has already been a great deal of work reported in the literature
regarding the synthesis and catalytic applications of RuNPs. The catalytic properties of these
NPs are highly dependent on their surface properties and their size. The ability to predict and
control the size of the NPs produced is therefore of the utmost importance. Also, producing NPs
free of ligands and other surface contaminants can only be advantageous in catalysis. In this
respect, the ionic liquid route, which has been shown to produce RuNPs of a controlled size
without necessitating stabilising ligands or supports, seems promising. However, in this case
little is known about the stabilisation mechanism – is the surface really ligand and contaminant
free? This is the first question answered in this thesis, in Chapter 2. Following this we look at the
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possibility of extending the potential of ionic liquids to the controlled growth and stabilisation of
other catalytically active metals, namely nickel and tantalum, also in Chapter 2.
Ionic liquids are also reported as interesting media for catalysis, so performing catalysis
with NPs produced in situ is a very intriguing prospect. However, first we must discern how the
properties ionic liquid itself effect the outcome of the catalytic process. This question is
answered in Chapter 3 by performing a model homogeneous catalytic reaction, namely the
hydrogenation of 1,3-cyclohexadiene using an ionic Osborn-type rhodium catalyst, in different
IL media.
Finally, in Chapter 4, we perform the hydrogenation of several substrates using RuNPs
generated in situ, with precise size-control, and confirm the substantial influence that
nanoparticle size can have on the catalytic performance.
44
1.5 References
1. G. Schmid, ed., Nanoparticles: From Theory to Application, Wiley-VCH, Weinheim,

2004.
2. H. Bönnemann and K. S. Nagabhushana, in Surface and Nanomolecular Catalysis, ed. R.
M. Richards, CRC Press, Boca Raton, 2006, pp. 63-94.
4. D. Astruc, ed., Nanoparticles and Catalysis, Wiley-VCH, Wienheim, 2007.
5. A. Roucoux, J. Schulz and H. Patin, Chem. Rev., 2002, 102, 3757-3778.
6. A. Roucoux, A. Nowicki and K. Philippot, in Nanoparticles and Catalysis, ed. D. Astruc,
Wiley-VCH, Weinheim, 2007, pp. 349-390.
tel-00708600, version 1 - 15 Jun 2012
7. A. Roucoux and K. Philippot, in Handbook of Homogeneous Hydrogenation, eds. J. G.

de Vries and C. J. Elsevier, Wiley-VCH Weinheim, 2007, pp. 217-256.
8. G. A. Somorjai and J. Y. Park, Top. Catal., 2008, 49, 126-135.
9. H. Bönnemann and K. S. Nagabhushana, in Encyclopedia of Nanoscience and
Nanotechnology, ed. H. S. Nalwa, American Scientific Publishers, Stevenson Ranch, CA,
2004, pp. 777-813.
10. H. Bönnemann and K. S. Nagabhushana, in Metal Nanoclusters in Catalysis and
Materials Science: The Issue of Size-control, eds. B. Corain, G. Schmid and N. Toshima,
Elsevier, Amsterdam, 2007, pp. 21-48.
11. B. Chaudret, Top. Organomet. Chem., 2005, 16, 233-259.
12. B. Chaudret and K. Philippot, Oil & Gas Science and Technology-Revue De L Institut
Francais Du Petrole, 2007, 62, 799-817.
13. C. Amiens and B. Chaudret, Mod. Phys. Lett. B, 2007, 21, 1133-1141.
15. C. Bruneau and P. H. Dixneuf, eds., Ruthenium Catalysts and Fine Chemistry, Springer,
Berlin/ Heidelberg, 2004.
16. G. C. Vougioukalakis and R. H. Grubbs, Chem. Rev., 110, 1746-1787.
17. H. Nagahara, M. Ono, M. Konishi and Y. Fukuoka, Appl. Surf. Sci., 1997, 121, 448-451.
18. A. M. R. Galletti, S. Antonetti, S. Giaiacopi, O. Piccolo and A. M. Venzia, Top. Catal.,
2009, 52, 1065.
45
19. R. Schlögl, Angew. Chem. Int. Ed., 2003, 42, 2004-2008.

20. A. Miyazaki, L. Balint, K. Aika and Y. Nakano, J. Catal., 2001, 204, 364-371.
21. J. M. Basset and A. Choplin, J. Mol. Catal., 1983, 21, 95-108.
22. A. Theolier, A. Choplin, L. D'Ornelas and J. M. Basset, Polyhedron, 1983, 2, 119-121.
23. V. L. Kuznetsov, A. T. Bell and Y. I. Yermakov, J. Catal., 1980, 1980, 374-389.
24. A. Zecchina, E. Guglielminotti, A. Bossi and M. Camia, J. Catal., 1982, 74, 225-239.
25. C. Bianchini, V. Dal Santo, A. Meli, S. Moneti, M. Moreno, W. Oberhauser, R. Psaro, L.
Sordelli and F. Vizza, J. Catal., 2003, 213, 47-62.
26. M. Leconte, A. Theolier, D. Rojas and J. M. Basset, J. Am. Chem. Soc., 1984, 106.
27. E. Rodriguez, M. Leconte, J.-M. Basset, K. Tanaka and K.-I. Tanaka, J. Am. Chem. Soc.,
1988, 110, 275-278.
tel-00708600, version 1 - 15 Jun 2012
28. N. Kitajima, A. Kono, W. Ueda, Y. Moro-oka and T. Ikawa, J. Chem. Soc., Chem.
Commun., 1986, 674-675.
29. R. Berthoud, P. Delichere, D. Gajan, W. Lukens, K. Pelzer, J. M. Basset, J. P. Candy and
C. Coperet, J. Catal., 2008, 260, 387-391.
30. V. Hulea, D. Brunel, A. Galarneau, K. Philippot, B. Chaudret, P. J. Kooyman and F.
Fajula, Microporous Mesoporous Mater., 2005, 79, 185-194.
31. P. Moggi, G. Albanesi, G. Predieri and G. Spoto, Appl. Catal., A, 1995, 123, 145-159.
32. L. Y. Song, X. H. Li, H. N. Wang, H. H. Wu and P. Wu, Catal. Lett., 2009, 133, 63-69.
33. L. K. Kurihara, G. M. Chow and P. E. Schoen, Nanostruc. Mater., 1995, 5, 607-613.
34. R. Harpeness, Z. Peng, X. S. Liu, V. G. Pol, Y. Koltypin and A. Gedanken, J. Colloid
Interface Sci., 2005, 287, 678-684.
35. M. Zawadzki and J. Okal, Mater. Res. Bull., 2008, 43, 3111-3121.
36. X. P. Yan, H. F. Liu and K. Y. Liew, J. Mater. Chem., 2001, 11, 3387-3391.
37. S. H. Joo, J. Y. Park, J. R. Renzas, D. R. Butcher, W. Huang and G. A. Somorjai, Nano
Lett., 2010, 10, 2709-2713.
38. G. Viau, R. Brayner, L. Poul, N. Chakroune, E. Lacaze, F. Fievet-Vincent and F. Fievet,
Chem. Mater., 2003, 15, 486-494.
39. Q. C. Xu, J. D. Lin, X. Z. Fu and D. W. Liao, Catal. Commun., 2008, 9, 1214-1218.
40. S. Gao, J. Zhang, Y. F. Zhu and C. M. Che, New J. Chem., 2000, 24, 739-740.
41. B. Chaudret, C.R. Phys., 2005, 6, 117-131.
46
42. B. Chaudret, Actual. Chim., 2005, 33-43.

43. K. Philippot and B. Chaudret, C.R. Chim., 2003, 6, 1019-1034.
44. K. Pelzer, K. Philippot, B. Chaudret, W. Meyer-Zaika and G. Schmid, Z. Anorg. Allg.
Chem., 2003, 629, 1217-1222.
45. O. Vidoni, K. Philippot, C. Amiens, B. Chaudret, O. Balmes, J.-O. Malm, J.-O. Bovin, F.
Senocq and M. J. Casanove, Angew. Chem. Int. Ed., 1999, 38, 3736-3738.
46. K. Pelzer, O. Vidoni, K. Philippot, B. Chaudret and V. Colliere, Adv. Funct. Mater.,
2003, 13, 118-126.
47. A. Duteil, R. Queau, B. Chaudret, R. Mazel, C. Roucau and J. S. Bradley, Chem. Mater.,
1993, 5, 341-347.
48. C. Pan, K. Pelzer, K. Philippot, B. Chaudret, F. Dassenoy, P. Lecante and M. J.
tel-00708600, version 1 - 15 Jun 2012
Casanove, J. Am. Chem. Soc., 2001, 123, 7584-7593.

49. T. Pery, K. Pelzer, G. Buntkowsky, K. Philippot, H. H. Limbach and B. Chaudret,
ChemPhysChem, 2005, 6, 605-607.
50. K. Pelzer, B. Laleu, F. Lefebvre, K. Philippot, B. Chaudret, J. P. Candy and J. M. Basset,
Chem. Mater., 2004, 16, 4937-4941.
51. P.-J. Debouttiere, V. Martinez, K. Philippot and B. Chaudret, Dalton Trans., 2009,
10172-10174.
52. N. Mejias, A. Serra-Muns, R. Pleixats, A. Shafir and M. Tristany, Dalton Trans., 2009,
7748-7755.
53. A. Nowicki, Y. Zhang, B. Leger, J. P. Rolland, H. Bricout, E. Monflier and A. Roucoux,
Chem. Commun., 2006, 296-298.
54. A. Denicourt-Nowicki, A. Ponchel, E. Monflier and A. Roucoux, Dalton Trans., 2007,
5714-5719.
55. C. Hubert, A. Denicourt-Nowicki, A. Roucoux, D. Landy, B. Leger, G. Crowyn and E.
Monflier, Chem. Commun., 2009, 1228-1230.
56. J. Y. Lee, J. Yang, T. C. Deivaraj and H. P. Too, J. Colloid Interface Sci., 2003, 268, 77-
80.
57. J. Yang, J. Y. Lee, T. C. Deivaraj and H. P. Too, J. Colloid Interface Sci., 2004, 271,
308-312.
58. J. Yang, T. C. Deivaraj, H. P. Too and J. Y. Lee, Langmuir, 2004, 20, 4241-4245.
47
59. R. A. Sanchez-Delgado, N. Machalaba and N. Ng-A-Qui, Catal. Commun., 2007, 8,

2115-2118.
60. T. Tsukatani and H. Fujihara, Langmuir, 2005, 21, 12093-12095.
61. L. M. Rossi, G. Machado, P. F. P. Fichtner, S. R. Teixeira and J. Dupont, Catal. Lett.,
2004, 92, 149-155.
62. E. T. Silveira, A. P. Umpierre, L. M. Rossi, G. Machado, J. Morais, G. V. Soares, I. J. R.
Baumvol, S. R. Teixeira, P. F. P. Fichtner and J. Dupont, Chem.--Eur. J., 2004, 10, 3734-
3740.
63. M. H. G. Prechtl, M. Scariot, J. D. Scholten, G. Machado, S. R. Teixeira and J. Dupont,
Inorg. Chem., 2008, 47, 8995-9001.
tel-00708600, version 1 - 15 Jun 2012
and J.-M. Basset, J. Mater. Chem., 2007, 17, 3290-3292.

66. J. Huang, T. Jiang, B. Han, W. Wu, Z. Liu, Z. Xie and J. Zhang, Catal. Lett., 2005, 103,
59-62.
67. C. M. Ho, W. Y. Yu and C. M. Che, Angew. Chem. Int. Ed., 2004, 43, 3303-3307.
68. K. Pelzer, K. Philippot and B. Chaudret, Z. Phys. Chem., 2003, 217, 1539-1547.
69. S. Jansat, D. Picurelli, K. Pelzer, K. Philippot, M. Gomez, G. Muller, P. Lecante and B.
Chaudret, New J. Chem., 2006, 30, 115-122.
70. M. Tristany, B. Chaudret, P. Dieudonne, Y. Guari, P. Lecante, V. Matsura, M. Moreno-
Manas, K. Philippot and R. Pleixats, Adv. Funct. Mater., 2006, 16, 2008-2015.
71. I. Favier, S. Massou, E. Teuma, K. Philippot, B. Chaudret and M. Gomez, Chem.
Commun., 2008, 3296-3298.
72. A. Gual, M. R. Axet, K. Philippot, B. Chaudret, A. Denicourt-Nowicki, A. Roucoux, S.
Castillon and C. Claver, Chem. Commun., 2008, 2759-2761.
73. A. Gual, C. Godard, K. Philippot, B. Chaudret, A. Denicourt-Nowicki, A. Roucoux, S.
Castillon and C. Claver, ChemSusChem, 2009, 2, 769-779.
74. A. Spitaleri, P. Pertici, N. Scalera, G. Vitulli, M. Hoang, T. W. Turney and M. Gleria,
Inorg. Chim. Act., 2003, 352, 61-71.
48
75. M. Zahmakiran, M. Tristany, K. Philippot, K. Fajerwerg, S. Oezkar and B. Chaudret,

Chem. Commun., 2010, 46, 2938-2940.
76. J. Yang, J. Y. Lee, T. C. Deivaraj and H. P. Too, Colloids Surf., A, 2004, 240, 131-134.
77. S. Ozkar and M. Zahmakiran, J. Alloys Compd., 2005, 404, 728-731.
78. M. H. G. Prechtl, J. D. Scholten and J. Dupont, J. Mol. Catal. A: Chem., 2009, 313, 74-
78.
79. Q. C. Xu, J. D. Lin, J. Li, X. Z. Fu, Y. Liang and D. W. Liao, Catal. Commun., 2007, 8,
1881-1885.
80. J. R. Anderson, ed., Structure of metallic Catalysts, Academic Press, London, 1975.
81. J. Okal, Catal. Commun., 2010, 11, 508-512.
82. J. Garcia-Anton, M. R. Axet, S. Jansat, K. Philippot, B. Chaudret, T. Pery, G.
tel-00708600, version 1 - 15 Jun 2012
Buntkowsky and H. H. Limbach, Angew. Chem. Int. Ed., 2008, 47, 2074-2078.
83. C. M. Hagen, G. Vieille-Petit, G. Laurenczy, G. Suss-Fink and R. G. Finke,
Organometallics, 2005, 24, 1819-1831.
84. F. Su, L. Lv, F. Y. Lee, T. Liu, A. I. Cooper and X. S. Zhao, J. Am. Chem. Soc., 2007,
129, 14213-14223.
85. W. Yu, H. Liu, M. Liu and Z. Liu, J. Colloid Interface Sci., 1998, 208, 439.
86. M. Liu, W. Yu and H. Liu, J. Mol. Catal., 1999, 243, 120.
87. M. Liu, W. Yu, H. Liu and J. Zheng, J. Colloid Interface Sci., 1999, 214, 231.
88. J. Wang, J. Feng, R. Qin, H. Fu, M. Yuan, H. Chen and X. Li, Tetrahedron: Asymmetry,
2007, 18, 1643-1647.
89. F. Fache, S. Lehuede and M. Lemaire, Tetrahedron Lett., 1995, 36, 885.
90. F. Launay and H. Patin, New J. Chem., 1997, 21, 247.
91. F. Launay, A. Roucoux and H. Patin, Tetrahedron Lett., 1998, 39, 1353.
92. H. P. Kormann, G. Schmid, K. Pelzer, K. Philippot and B. Chaudret, Z. Anorg. Allg.
Chem., 2004, 630, 1913-1918.
93. N. Yan, C. Zhao, C. Luo, P. J. Dyson, H. Liu and Y. Kou, J. Am. Chem. Soc., 2006, 128,
8714-8715.
94. V. Matsura, Y. Guari, C. Reye, R. J. P. Corriu, M. Tristany, S. Jansat, K. Philippot, A.
Maisonnat and B. Chaudret, Adv. Funct. Mater., 2009, 19, 3781-3787.
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50
II
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Chapter 2
Generation and Stabilisation

of Transition Metal
Nanoparticles in
Imidazolium-Based
Ionic Liquids
51
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52
Chapter 2 Generation and Stabilisation of Transition Metal NPs in Imidazolium ILs
Chapter 2
Generation and Stabilisation of Transition Metal
Nanoparticles in Imidazolium-Based Ionic Liquids
2.1 Introduction .................................................................................................................................... 55
2.2 The stabilisation of ruthenium nanoparticles in ionic liquids ........................................................ 57
2.2.1 In situ evidence of surface hydrides .......................................................................................... 59

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2.2.1.1 H/D exchange by gas phase 1H NMR spectroscopy ......................................................... 60
2.2.1.2 Reaction with ethylene...................................................................................................... 61
2.2.2 Stabilising effect of the surface hydrides................................................................................... 63
2.2.3 Evidence for close proximity between the RuNP surface and the alkyl chains......................... 64
2.2.3.1 [C1C4//Im][NTf2], IL2: ....................................................................................................... 65
2.2.3.2 [C1BzIm][NTf2], IL3: ........................................................................................................ 67
2.2.4 Role of the continuous 3-D network of ionic channels in the isolation of RuNPs .................... 68
2.2.5 The effect of water..................................................................................................................... 69
2.2.6 Conclusion ................................................................................................................................. 71
2.3 Synthesis and stabilisation of nickel nanoparticles in ionic liquids ............................................... 73
2.3.1 Size-controlled synthesis of NiNPs ........................................................................................... 75
2.3.1.1 Decomposition in [C1C6Im][NTf2], [C1C8Im][NTf2] and [C1C10Im][NTf2] ..................... 75
2.3.1.2 Effect of temperature ........................................................................................................ 76
2.3.1.3 Influence of the length of the alkyl side chains ................................................................ 77
2.3.1.4 Comparison with RuNPs .................................................................................................. 77
2.3.2 Spontaneous decomposition on solvation.................................................................................. 78
2.3.3 Avoiding carbene formation ...................................................................................................... 82
53
2.3.4 Conclusion ................................................................................................................................. 84
2.4 Tantalum nanoparticles .................................................................................................................. 86
2.4.1 Synthesis in pure [C1C4Im][NTf2] ............................................................................................. 87
2.4.2 Addition of a co-solvent ............................................................................................................ 88
2.4.3 Increasing the chain length ........................................................................................................ 90
2.4.4 High resolution electron microscopy of TaNPs......................................................................... 90
2.4.5 Conclusion ................................................................................................................................. 91
2.5 Experimental Section ..................................................................................................................... 92
2.5.1 Materials and Methods .............................................................................................................. 92
2.5.4 Transition Electron Microscopy ................................................................................................ 97

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2.5.6 Hydrogenation of Ethylene by RuNPs in the IL ........................................................................ 97
2.5.7 H-D exchange ............................................................................................................................ 99
2.5.8 TON calculations ....................................................................................................................... 99
2.6 References .................................................................................................................................... 100
54
2.1 Introduction
During the last decade, the use of ionic liquids (ILs) has become a very popular route for
the generation of transition metal nanoparticles (NPs).1 The main advantage over traditional
solvents is that IL media are able to stabilise NPs in the absence of further additives such as
ligands, inhibiting metal coalescence to the bulk.2 For catalytic applications this is good news, as
the surface of the resultant NPs is ligand-free and therefore completely available for the
coordination of substrates. However, the question of precisely how ILs stabilise transition metal
NPs remains under debate.
Very little data is available in the literature to explain this phenomenon, and much is
speculative.3 Many describe “electrosteric stabilisation” whereby an electrostatic double layer
of anions and cations surround the electropositive NP surface.4, 5
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These NP-IL aggregates are

therefore separated by electrostatic repulsion, Derjaugin–Landau–Verwey–Overbeek-type forces
(DLVO), Scheme 1.3, 6-8
A small angle X-ray scattering (SAXS) study of various ILs in the
presence and absence of IrNPs has provided evidence to suggest the ordering of the ions around
the NP surface, corroborating the DLVO model.9
Scheme 1. An electrosterically stabilised nanoparticle in tetrabutyl ammonium chloride.10
Surface enhanced Raman spectroscopy (SERS) has been used to probe the interactions
between an imidazolium based IL and the surface of AuNPs generated in situ, providing
evidence for a planar interaction between the imidazolium ring and the NP surface, but very little
interaction between the anion and the NP.11 This is clearly contradictory to the much discussed
DLVO model. Furthermore, the coordination of the IL moieties to the NP surface could be
55
envisaged. Indeed, this has been evidenced for IrNPs synthesised by reduction of an ionic
organometallic complex in the ionic liquid [C1C4Im][BF4]. Subsequent treatment of the mixture
under deuterium, followed by 2H NMR analysis showed that hydrogen-deuterium exchange had
occurred on the imidazolium ring, Figure 1. This was used to evidence the formation of labile N-
heterocyclic (NHC) ligands, namely imidazolylidene, however given the acidic nature of the C 2-
H of the imidazolium ring this exchange would be facile and therefore the conclusion seems
speculative.12, 13
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Figure 1. 2H NMR spectrum of [C1C4Im]+ after treatment under D2 in the presence of IrNPs.12, 13
If these literary observations are believed, it seems that the stabilisation of NPs is a
complex issue, dependent on the nature of both the metal and the IL in question, not to mention
the synthetic route. To the best of our knowledge, no stabilisation mechanism has been proposed
for RuNPs in ILs to date. Consequently, in this chapter we investigate and discuss the
stabilisation mechanism for RuNPs in imidazolium ILs. Following this, the possibility of
generalising our findings to other transition metals is explored.
56
2.2 The stabilisation of ruthenium nanoparticles in ionic liquids
ILs, particularly those based on imidazolium, can be thought of as “supramolecular

fluids”, since in the liquid state they display a high degree of self-organisation. In these media,
ionic channels, formed by extended hydrogen-bond networks between the anions and cation
headgroups, coexist with non-polar “pockets”, created by the grouping of lipophilic alkyl side
chains, illustrated in Scheme 2.14-17
O H
O
S CF3 N
S N
F3C O H
O N H
H O
O
CF
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S 3
S N
N N F3C O
O
H
H H
CF3 H
O N
S
O N
O N
H CF3
N H
S
O H S
F3C O O
N
N
H S
O O
CF3
Scheme 2. Representation of intermolecular organisation in [C1C4Im][NTf2] in the liquid state: ionic channel linked
through H-bonds and consequent aggregation of alkyl chains.
This structural organisation of ILs can be used as an entropic driver for the spontaneous
self-assembly of nanoscale structures with long-range order.18 For this purpose, ILs have already
been used as media for the synthesis of some zeolite-related, microporous aluminophosphates or
ordered mesoporous materials in which ILs have served both as solvents and as structure-
directing agents.19
This segregation of polar and non-polar domains in imidazolium-based ILs dictates their
interactions with given solutes. Polar or ionic species, e.g. water, will preferentially dissolve in
57
the polar regions, whereas non-polar lipophilic compounds, e.g. hexane, will be concentrated in
the non-polar pockets.20
The synthesis of RuNPs by direct reduction RuO2 is reported, however this leads to the
presence of an oxide surface and/or strongly coordinating water ligands, which are difficult to
remove.21 The decomposition of ( 4-1,5-cyclooctadiene)( 6-1,3,5-cyclooctatriene)ruthenium(0),
Ru(COD)(COT), by hydrogen is a well known route to obtaining RuNPs, in both organic,22, 23
and ionic liquid media, Scheme 3.24-26 The main advantage of this halogen-free synthesis is that
the only side product, cyclooctane, is easily removed under vacuum. This organometallic
complex is non-polar and therefore when dissolved in an ionic liquid is concentrated in the
aforementioned non-polar pockets. This principle has already been exploited in our laboratory in
the size-controlled synthesis of RuNPs from Ru(COD)(COT) in various imidazolium ILs (1-
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alkyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide [C1CnIm][NTf2], n = 2, 4, 6, 8,

10).26 The local concentration of organometallic precursor, therefore number of Ru atoms, is
controlled by the size of these non-polar pockets, which in turn is dictated by the length of the
alkyl side chain. As a result, after decomposition under molecular hydrogen the resulting RuNPs
are small, with narrow size distributions. Their mean diameter varies with the length of the
imidazolium alkyl side chain, as seen in Figure 2. It is worth nothing that for both short (n = 2)
and long (n = 10) alkyl chains, size control is not achieved, due to lack of domain segregation for
the former and interconnection of the non-polar pockets for the latter.
Scheme 3. The synthesis of RuNPs from the decomposition under H 2 of Ru(COD)(COT) in ILs
58
Interconnexion of
Linear crystal growth non-polar domains
Polar medium
in non-polar domains
2.5 2.3 ±0.8
nm
2
1.9 ±0.6
nm
Mean size (nm)
1.5
1.1 ±0.2 RuNP

1 nm
Nonpolar domains
0.5
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(lit.)
0
0 2 4 6 8 10
Alkyl chain length (n carbons) 3
Figure 2. Graph to show the variation in RuNP size with repect to imidazlolium side alkyl chain length. (circles)26
Also plotted, experimentally measured mean diameter of non-polar domains with respect to alkyl chain length.
(squares) 15
The RuNP/IL solutions obtained via this method remain stable indefinitely under inert
atmosphere and ambient conditions, with no coalescence or precipitation observed. Given the
apparent absence of ligands, the reason behind this stability is unknown.
When carried out at low temperatures (0 °C) in the absence of stirring in 1-butyl-3-
methylimidazolium bis(trifluorosulphonyl)imide, [C1C4Im][NTf2], this procedure consistently
yields the smallest small NPs with the narrowest size distribution (mean size: 1.1 ± 0.2 nm
calculated from TEM images realised in situ).25 These conditions have been replicated
throughout this work, to obtain fresh IL-stabilised colloidal solutions, on which NMR and mass
spectroscopy experiments have been performed, to determine the key points in their stabilisation.
2.2.1 In situ evidence of surface hydrides
The presence of surface hydrides has already been reported on RuNPs in organic
solvents.23, 27-29 Furthermore, in heterogeneous catalysis, it is well-known that under hydrogen
atmosphere, the surface of late transition metals is covered by hydrides.30-32 In ILs, is such
59
coverage still possible? Given the current and general stabilisation theory concerning NPs in ILs,
(strong interaction between the NPs and anion or cation, DLVO model),6, 33
the formation of
surface hydrides could be inhibited. Surface hydrides on NPs in ILs have to the best of our
knowledge never been reported or envisaged.
a) HD 200Hz
H2 1200Hz (3)
(2)
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(1)
10 9 8 7 6 5 4 3 2 1 0 ppm
b)
C2 -D C4,5 -D
(3)
(2)
0.40
0.75
3.00
C4,5 -H methyl-H
C2 -H
methyl-H
C2 -H C4,5 -H
(1)
9 8 7 6 5 4 3 2 1 ppm
1
Figure 3a) H NMR of gas phase (1) pure H2, (2) gas phase after 1 hour dynamic vacuum and 1 day under
deuterium, (3) gas phase after 4 hours dynamic vacuum and 4 days stirring under deuterium; b) (1) 1H NMR
spectrum of IL after NP formation under H2 and evacuation of H2 and cyclooctane, (2) 1H and (3) 2H NMR spectra
of the reaction medium after addition of D2.
2.2.1.1 H/D exchange by gas phase 1H NMR spectroscopy

Due to the low solubility of H2 in ILs,34 the remaining H2 dissolved after decomposition
of Ru(COD)(COD) is totally removed under high vacuum. A solution of freshly prepared RuNPs
in [C1C4Im][NTf2] (IL1) was thus first treated under dynamic vacuum (10-5 mbar, 1 h or 4 h) and
then stirred under deuterium (1 bar at 25 °C, 1 day or 4 days). The gas phase was then expanded
60
into an airtight Young NMR tube. The 1H NMR spectrum obtained exhibited a broad peak,
(w½ = 1200 Hz) corresponding to H2, superimposed with a finer peak (w½ = 200 Hz)
corresponding to HD, the intensity increasing with reaction time, Figure 3a. This is in agreement
with previous findings in the literatue for RuNPs in organic solvents,28 or supported on oxides,31,
32
and allows us to assign the HD desorption as resulting from deuterium activation on RuNPs
and recombination with bound H atoms, as observed on metal surfaces, Scheme 4.
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Scheme 4. H-D exchange on the RuNP surface.
The fact that there is ~ 60 % H/D exchange on positions 2, 4 and 5 of the imidazolium
ring, as shown by 1H and 2H NMR spectra of the IL, Figure 3b, could suggest that the HD
formed is due to this exchange and not from putative surface hydrides. However, when the ionic
liquid is treated under D2 in the absence of RuNPs, no H/D exchange is observed. The observed
H/D exchange must inevitably involve RuNP surface. To prove the presence of these surface
hydrides, further experiments have been performed characteristic of metal surface reactivity,
such as hydrogenation, as detailed in the following section.
2.2.1.2 Reaction with ethylene
The reaction of alkenes with PVP- (polyvinylpyrrolidone-) and ligand-stabilised RuNPs
has recently been used to quantify the surface hydrides.29 A similar approach was transposed to a
solution of RuNPs in IL1. In the following discussion, the RuNPs were generated in 2mL of IL1
from 86 μmol of Ru(COD)(COT). Given that the dispersion of NPs, (D, i.e the ratio surface
atoms Ns per total number of atoms Nt, D = Ns/Nt), is correlated to their size,30, 35, 36 we could
estimate that for RuNPs of 1.1 nm the dispersion is 83 %, corresponding for 86 μmol of
Ru(COD)(COT) to NS ≈ 71 μmol of Ru surface atoms. This IL1-stablised RuNP solution was
flushed overnight with argon to remove dissolved hydrogen. Then the solution was stirred under
an ethylene atmosphere (105.5 mbar) at 25°C. After 24 h of reaction the system reached
equilibrium, i.e. the pressure remained constant. In the gas phase, analysed by GC, 11 ± 1 μmol
of ethane and 0.1 μmol of iso-butane were found, corresponding to at least 22 ± 1 μmol of
61
surface hydride: (C2H4 + H2 C2H6). Note that butenes (trans- and 1-) were also observed
(0.2 μmol), however no hydrogen would be consumed in their formation. In summary, IL1-
stabilised RuNPs reacted with ethylene at room temperature to give ethane (hydrogenation) and
surface-bound alkyl species (homologation).37, 38
To quantify the total amount of surface-bound alkyl species, the gas phase was evacuated
and substituted by H2 (120 mbar) and the medium was heated at 100 °C for 12 h. In the gas
phase, methane (4.6 μmol), ethane (8.2 μmol), propane (2.7 μmol), n-butane (1.0 μmol) and n-
pentane (0.1 μmol) were detected, corresponding to at least a further 16 μmol of hydrides.
Knowing the total amount of surface Ru atoms available (65 μmol) and the number of surface
hydrides consumed in all the hydrogenation reactions (38 μmol) it is possible to calculate the
ratio of hydrides per surface Ru atom: c.a. 0.6 H /RuS.* The combination of these results provides
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substantial evidence for the existence of surface hydrides on the IL1-stabilised RuNPs, although
the level of error in the quantitative results means that it is difficult to establish accurately the
quantity. The amount of H adsorbed on PVP- and ligand- stabilised RuNPs in organic solvent is
reported between 1.1-1.3 H/RuS,28and between 1 and 2 H/RuS for RuNPs supported on oxides.31,
32
Note that if the IL1-stabilised solutions of RuNP were treated under high vacuum (10-6 mbar)
overnight at room temperature, instead of being flushed with argon to remove the dissolved H2,
ethylene conversion is negligible. This suggests that the surface hydrides on RuNPs are labile
and almost completely desorbed under high vacuum.39-41
Indeed, hydrides bound to metal surfaces are known to be labile and the dissociation of
H2 adsorbed onto a metal surface is reversible: M + H2 ↔ MH2 ↔ 2 M–H. In the case of Ru,
about 2/3 of the total amount of surface hydrides are reversibly bound. These H species
correspond to more weakly adsorbed hydrogen on the surface, which is easily removed by
treating the sample under vacuum at 25 °C.31, 32.This explains why the hydrogenation of ethylene
(in the absence of hydrogen) does not occur over NPs previously treated under high dynamic
vacuum (10-5 mbar) for an extended period (12 h), as very few surface hydrides remain.39-41 It is
nevertheless very interesting that the presence of hydrides on ruthenium particles in ionic liquids
is confirmed, since this is in agreement with the presence of these nanoparticles in uncharged
lipophilic domains.
*
For calculations see experimental section 2.5.6
62
2.2.2 Stabilising effect of the surface hydrides

In order to ascertain the stabilising effect of hydrogen, two aliquots of the RuNP/IL1
solution were taken and stirred at 100 °C for a period of 24 h, either under H2 or under Ar
(1 bar). The resulting solutions were analysed by TEM. For the aliquot heated under H2, the
mean size of the RuNPs increased to 1.4 ± 0.7 nm, and for the aliquot heated under argon, the
mean size increases to 2.2 ± 0.8 nm. This difference in size increase with the gas atmosphere
demonstrates the inferior stability of the particles when heated under argon compared to under
H2. In addition, when the RuNP/IL1 solution was treated under high vacuum (10-6 mbar)
overnight at room temperature, the TEM images show an increase in size from 1.1 ± 0.2 nm to
1.7 ± 0.4 nm, Figure 4. From these results, it appears that there is less coalescence of the RuNPs
when heated under H2 at 100 °C than under argon at the same temperature. This may be
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explained by the elimination of the hydrogen atoms reversibly bound to the metal surface, which
is made likely by heating under an inert atmosphere or treatment under high vacuum. In
conclusion, the presence of surface Ru–H stabilises the RuNPs. The results of these stability
experiments are also consistent with the lability of the hydrides which can be desorbed from the
nanoparticles in vacuo or at 100 °C.
20nm
20 nm
120 20 nm
100 RuNPs
H2
Ar
80 Vacuum
Frequency
20 nm
60
40
20
0
0 1 2 3 4 5 6
Size (nm)
Figure 4. TEM images captured in situ in ionic liquids and comparative size histograms of RuNPs/[C1C4Im][NTf2]
(1.1 ± 0.2 nm) heated to 100 °C for 24h under H2, under Ar and kept under dynamic vacuum (10-5 mbar) for 24 h at
25 °C.
63
In further tests, samples of these NP solutions were stirred under pure CO or pure O2
atmosphere (1 bar) during a period of 24 h. It was seen that under O2 the NPs underwent slight
coalescence, growing to a size of 1.5 ± 0.4 nm, and those resulting from stirring under CO
exhibited an interesting bimodal size distribution centred at 1.3 and 1.8 nm, Figure 5. It is worth
noting that the number of RuNPs smaller than 1 nm increases probably due to the formation of
ruthenium carbonyl clusters. Due to the low concentration of RuNPs in solution, (CO) for
coordinated CO was not observed by IR spectroscopy. In comparison with H2, O2 and CO appear
to have a destabilising effect, inducing slight agglomeration.
70
50
60
40 RuNP size CO
50
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RuNP size O2
Frequncy
Frequency
30 40
30
20
20
10
10
0 0
0.5 1.0 1.5 2.0 2.5 3.0 0.5 1.0 1.5 2.0 2.5
Size/nm Size/nm
Figure 5. Size distribution histograms of RuNPs formed in IL1 after treatment under dry O 2 (left) and CO (right).
2.2.3 Evidence for close proximity between the RuNP surface and the alkyl chains
The fact that in [C1CnIm][NTf2], the non-polar domains control the local concentration of
Ru(COD)(COT) and consequently the size of RuNPs generated in situ, could allow us to
consider them as nanoreactors in which the phenomenon of crystal growth occurs.26 If the RuNPs
are indeed encapsulated in these non-polar pockets, it would be expected that the side alkyl
groups of the ILs be in close proximity or even in interaction with the RuNP surface.
To demonstrate this, the RuNPs were synthesised under deuterium instead of hydrogen
(following otherwise identical reaction conditions), since an H-D exchange on the side group of
the IL would prove the existence of the NPs in these domains. In the case of IL1, 2H NMR
spectra show us that, as expected, deuteration occurs at all positions on the imidazolium ring due
to the relatively high acidity of these protons. Furthermore, one small peak is apparent at
~1.5 ppm, which may correspond to deuteration at position C8, i.e. the penultimate carbon of the
butyl chain, however this is not irrefutable. The intensities of the peaks in the 1H NMR spectrum
64
were reduced by roughly 30 % at positions C2, C4 and C5, but no significant reduction in
intensity was noted for any of the alkyl peaks. ESI mass spectra indicate the formation of mono-,
di-, tri- and a trace amount of tetra-deuterated species. This is in agreement with the higher
reactivity of the hydrogen bound to the imidazolium ring than to the alkyl side chain. Note that,
5
in contrast to findings for IrNPs, where the deuteration was found mainly at position C2, for
RuNPs deuterium incorporation occurs equally at positions C2, C4 and C5 on the imidazolium
ring.
This experiment was then carried out in ILs with unsaturated functional side groups: 1-
(but-3-enyl)-3-methylimidazolium bis(trifluorosulphonyl)imide [C1C4//Im][NTf2], IL2 and 1-
benzyl-3-methylimidazolium bis(trifluorosulphonyl)imide [C1BzIm][NTf2], IL3. These
functionalised side groups are more susceptible to H-D exchange.
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2.2.3.1 [C1C4//Im][NTf2], IL2:

TEM images of nanoparticles synthesised in IL2 under deuterium at 0°C show that the
nanoparticle size distribution is similar to that of RuNPs synthesised in IL1. This result provides
supplementary evidence to suggest that the size is dictated by the length of the alkyl chain and
that the RuNPs are formed in the non-polar domains of the ILs, Figure 6.
C4C1Im NTf2
140 C4//C1Im NTf2
130
120
110
100
90
frequency
80
70
60
50
20 nm
40
30
20
10
0
0.0 0.5 1.0 1.5 2.0 2.5
size/ nm
Figure 6. Comparative size distribution curves for RuNPs synthesised in IL1 and IL2 and TEM image captured in
situ IL for RuNPs synthesised in IL2
For IL2, 2H NMR spectra show that deuteration takes place at positions C8 and C9, i.e. the
olefinic positions, as well as at position C2. Surprisingly, isotopic exchange is observed neither at
65
positions C4 and C5 of the imidazolium ring, nor at positions C6 and C10. Instead, and more
interestingly, a new set of peaks appears at high field, corresponding to a deuterated butyl group
due to the deuteration and reduction of the C8=C9 double bond, Figure 7. Further heating of this
solution under deuterium at 50 °C for 12 h led to a pronounced growth of all peaks already
deuterated, but no deuteration at other positions. The intensities of the peaks in the 1H NMR
spectrum of IL2 after reaction are reduced significantly at positions C2, C8 and C9 indicating that
24 % of the ionic liquid had undergone at least one H-D exchange and NMR and ESI mass
spectra indicate that around a further 15 % had been reduced to a deuterated butyl species
corresponding to a TON of ~16 with respect to Rus at 0 °C.† Also, besides the peaks due to IL1
(labelled * in Figure 8), new peaks appeared (labelled ° in Figure 8) in the Csp2 and Csp3 regions,
corresponding to IL2isom in which there had been an isomerisation of the butenyl chain,
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Scheme 5.
Figure 7 a) 1H NMR spectrum of [C1C4//Im][NTf2], neat IL2; b) 2H NMR spectrum of IL2 after RuNP formation at
0°C under deuterium; c) 2H NMR spectrum of IL2 after RuNP formation at 50 C under deuterium; d) 1H NMR
spectrum of [C1C4Im][NTf2], neat.
†
ESI mass spectra and calculations of TON are given in the experimental section 2.5
66
Scheme 5 Isomerisation of IL2

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Figure 8. 1H NMR spectra of neat IL2; IL2 after RuNP formation at 0 °C under deuterium; neat IL1.
2.2.3.2 [C1BzIm][NTf2], IL3:

The TEM images of RuNPs synthesised in IL3 under deuterium at 0 °C showed a size
distribution centred at 3.2 ± 0.7 nm. The larger size is expected due to the higher degree of 3-
dimensional supramolecular organisation of ILs with the side chain substituted by an aryl group,
provoking π-π and π-cation interations.42
In the 2H NMR spectra of IL3 after reaction, deuterium incorporation at position C2, and
positions C4 and C5 of the imidazolium ring and/or the aromatic positions is observed. Also a
new set of aliphatic peaks appears at high field centred at 1.4 ppm corresponding to a reduced
methylenecyclohexyl group, Figure 9. The intensities of the peaks in the 1H NMR spectrum of
IL3 after reaction are reduced at positions C2, C4 and C5 but even more significantly at the
aromatic positions, where peak intensity is reduced by 35 %. Indeed, from 1H NMR and
electrospray ionisation (ESI) mass spectra, it appears that around 60 % of the ionic liquid
undergoes at least one H-D exchange, around 30 % of which is transformed into the deuterated
methylenecyclohexyl CH2C6DxH11-x form, with a corresponding TON of ~64 with respect to
67
Rus.‡ Further heating of this solution under deuterium at 50 °C for 12 h led to a pronounced
growth of all peaks mentioned in the 2H NMR spectrum.
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Figure 9. 2H NMR spectra of [C1BzIm][NTf2], IL3, after RuNP formation at 0 °C under deuterium (lower) and after
a further 12 h of heating to 50 °C under deuterium (upper).
The hydrogenation of an aryl substituent, which does not occur with any molecular
ruthenium complexes derived from Ru(COD)(COT), must occur on the nanoparticle surface.43
This observed reduction therefore clearly demonstrates the proximity between the aryl groups of
the ILs and the RuNP surface.
During the formation of RuNPs under deuterium in both IL2 and IL3, the side groups of
the imidazolium rings are saturated with deuterium. In neither case is the C2 position the primary
site for H–D exchange, in contrast to literature results.13 Furthermore, in the case of IL2, no
exchange is observed at positions C4 and C5. Note that no exchange occurs at either position C6
or C10 in either IL. These results indicate that the side chains of the imidazolium are situated in
close proximity of the RuNP surface, where activation of deuterium and C-H occurs.
2.2.4 Role of the continuous 3-D network of ionic channels in the isolation of RuNPs
Addition of coordinating substrates, such as water, solvate the rigid ionic channels of the
IL through the formation of strong hydrogen bonds with the anions and also weaker hydrogen
bonds between the H bound to the C2 of the cation.20, 44, 45 Solvation of this ionic network alters
the structure of the ionic liquid causing aggregation of the non-polar domains.46-49 The following
question arises: what happens to the RuNPs if the structure of the IL is disrupted?
‡
ESI mass spectra and calculations of TON are given in the experimental section 2.5
68
When, under argon atmosphere, an amount of water is added to a stable RuNP/IL

suspension, TEM images show agglomeration of the NPs after treatment, Figure 10, supporting
the fact that the RuNPs are originally isolated within nonpolar pockets by this network. It is clear
that before coalescing, NPs must agglomerate, so preventing agglomeration has an indirect
influence on stability.
40
30
Frequency
20
10
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0
0.5 1.0 1.5 2.0 2.5 3.0
Size/nm
Figure 10. TEM image of RuNPs in IL1 after treatment with water and resultant size distribution histogram.
2.2.5 The effect of water

As the destructive nature of water on the IL structure and the hydrophobic properties of
the RuNPs formed in situ in ionic liquids has been demonstrated, this gives rise to the question of
what happens when RuNPs are formed in an IL in the presence of water.
Ionic liquids based on the [NTf2] anion are hydrophobic due to the perfluorinated nature
of this anion and therefore immiscible in water. The maximum solubility of water in
[C1C4Im][NTf2] is reported as 26 % molar at ambient temperature (299 K). Two different tests
were performed:
1) Firstly, a solution of Ru(COD)(COT) in IL1 was prepared, then an amount of pure
heavy water (D2O) (3% molar, 30% molar or large excess of water) was added to
destroy the structure of the ionic liquid before decomposition of Ru(COD)(COT)
under H2 (4 bars) at 0 °C.
2) Secondly, IL-heavy water mixtures were prepared (3% molar, 30% molar or an
excess of water), into which was dissolved Ru(COD)(COT) before decomposition
under H2 (4 bars) at 0 °C.
In neither case did the presence of water provoke the decomposition or oxidation of
Ru(COD)(COT), which may be indicative of the segregation of the Ru(COD)(COT) and water
69
by their solvation in different domains of the ionic liquid. TEM images of the NPs obtained are
shown in Figure 11.
a) IL1/Ru(COD)(COT) + 3%D2O + H2 à d) IL1/3%D2O + Ru(COD)(COT) + H2 à
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b) IL1/Ru(COD)(COT) + 30%D2O + H2 à e) IL1/30%D2O + Ru(COD)(COT) + H2 à
c) IL1/Ru(COD)(COT) + excess D2O + H2 à f) IL1/excessD2O + Ru(COD)(COT) + H2 à
Figure 11. TEM images of solutions of RuNPs synthesised in ILs in the presence of water.
70
As can be seen in the TEM images in Figure 11 the presence of water has a significant
impact on the organisation of the resultant NPs. For the solutions prepared with water below the
limit of solubility, whether the water be added before or after the Ru(COD)(COT) the same
pattern is observed. For 3 % water (molar), RuNPs of around 2 nm group in circular aggregates
of around 20-30 nm in diameter (a and d in Figure 11), and for 30 % water RuNPs also of around
2 nm, group in larger circular aggregates of 30-50 nm (b and e in Figure 11). NPs formed from
the dissolution of Ru(COD)(COT) into water-saturated IL1 before decomposition exhibit the
same type of agglomeration of NP, here the diameter of the circular aggregates varying from
between 30 and 150 nm (f in Figure 11). This findings support the idea of “water-pools” in wet
ILs i.e. micellar-type aggregates of water, as through diffusion measurements water has found to
not be completely miscible on the microscale.47 In this case, RuNPs appear to decorate the water-
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IL interface, known as the “Pickering effect”.50

In the final case, when excess water was added to the preformed solution of
Ru(COD)(COT) in IL1 and the subsequent mixture exposed H2 for NP generation, clear phase
separation is apparent from the TEM image, with the NPs uniquely in the IL phase, § and again
concentrated at the IL-water interface.
2.2.6 Conclusion
The phenomenon of crystal growth of RuNPs generated in situ from Ru(COD)(COT), in
imidazolium-based ILs is found to be controlled by the size of non-polar domains created by the
grouping of lipophilic alkyl chains. Close proximity of the RuNPs to the non polar R group of
the cation is evidenced by in situ labelling experiments (deuteration and reduction), thus
corroborating the hypothesis that RuNPs are surrounded by these non-polar pockets. Addition of
water, destroying the ionic network, induces agglomeration of the RuNPs, supporting the fact
that the RuNPs are originally isolated within non-polar pockets by the 3-D network of ionic
channels. Furthermore, the presence of surface hydrides and their role in the stabilisation of the
nanoparticles is demonstrated. Finally, the RuNPs are shown to be hydrophobic.
As already mentioned, literary results give conflicting views on the mechanism for the
growth and stabilisation of transition metal nanoparticles in ionic liquids, leading to the
conclusion that this could depend on the nature of the metal, its precursor complex, the synthetic
§
Given the relative volatility of water with respect to the IL, we assume the light regions correspond to water, which
under the electron beam and UHV conditions will evaporate.
71
route and/or the ionic liquid used. We have already demonstrated the growth, size control and
stabilisation mechanism of RuNPs from the decomposition under H2 of the zero-valent
organometallic ruthenium compound Ru(COD)(COT) in imidazolium ionic liquids.
This leads to the question of whether the same would be true of NPs generated in the
same way from an analogous organometallic compound of another metal. For this reason, in this
chapter we investigate the possibility of generalising these findings to the generation of nickel
nanoparticles, NiNPs, as the organometallic complex bis(1,5-cyclooctadiene)nickel, Ni(COD)2,
analogous to Ru(COD)(COT), is commercially available.
Furthermore, as zero-valent ogranometallic complexes are often difficult to come by,
particularly those of the early transition metals, it may be interesting to look at the reductive
decomposition of alkyl-metals. Therefore, the generation of tantalum nanoparticles, TaNPs from
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decomposition in IL media of the well-known Schrock complex,

tris(neopentyl)(neopentylidene)tantalum, is also investigated in this chapter.
72
2.3 Synthesis and stabilisation of nickel nanoparticles in ionic liquids
Nickel is one of the most abundant and therefore least costly of the catalytically active
late transition metals – 17 USD/kg (nickel) vs. 5340 USD/kg (ruthenium) – so presents a clear
economic advantage if its catalytic potential is exploited. Furthermore, bulk nickel being
ferromagnetic, magnetic nanomaterials often exhibit interesting optical and photoelectronic
properties,51 as well as being superparamegnetic. Their magnetic properties vary with size, shape
and composition and therefore magnetic measurements are often used as complementary
characterisation.
NiNPs have been prepared by the reduction of organometallic precursors such as nickel
tetracarbonyl (Ni(CO)4), bis-(cyclopentadienyl) nickel, (Ni(C5H5)2), bis-(acetylacetate) nickel
(Ni(acac)2),52 and bis-(1,5-cyclooctadiene)nickel (Ni(COD)2,53-57 in different stabilising media.
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For the purpose of our work Ni(COD)2 is chosen due firstly to its zero-valence and also to the
fact that the by-products of decomposition are light hydrocarbons that are easily removed under
vacuum and will not react with the surface of the NiNPs, unlike any halide or carbonyl precursor.
Furthermore, this complex is analogous to Ru(COD)(COT), facilitating the comparison of
results.
The aim of this section is to (1) determine whether, as for RuNPs, the size control of
NiNPs generated in situ in ILs may be achieved through use of the intrinsic 3-D structure, and
(2) determine the stabilisation factors of the resultant NiNPs.
H2 (3 bar), 70 °C evaporation THF

Ni NiNPs
THF addition of MeOH or pentane
PVP
Figure 12. Typical synthesis of PVP-stabilised NiNPs dispersed in organic solvent (Chaudret’s method). TEM
image of PVP-stabilised NiNPs dispersed in MeOH and subsequent size distribution histogram.53
73
Ni(COD)2, when decomposed under hydrogen in organic solvents such as THF in the
presence of hexadecylamine (HDA) as the stabiliser ligand or polyvinylpyrrolidone (PVP) as
polymer support,53, 54 produces NiNPs of a face centred cubic structure with a size distribution
centred around 4 – 5 nm, as found by Chaudret’s group. Cyclooctane is produced as a side
product. These NPs may be removed from the media by evaporation of the solvent and
homogenised by redispersion into other solvents, such as methanol or pentane, as seen in Figure
12. The NiNPs display a magnetisation value comparable to that of bulk Ni, although the
magnetic behaviour may be altered by adding more coordinating substrates to the medium, e.g.
CO.53, 54
Clearly research into NiNPs is well advanced, however the challenge remains to generate
sizes of less than 4 nm, which have not yet been successfully prepared from organometallic
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precursors. To our knowledge the smallest recorded NiNPs are 2.5 nm, prepared by means of
laser electrodispersion techniques.58
H2 (4bar), 75 °C
Ni NiNPs
C1CnIm NTf2
Benzene
Figure 13 TEM micrographs and respective histograms showing the size-distribution of Ni nanoparticles prepared
and dispersed in [C1C4Im][NTf2] [a], [C1C8Im][NTf2] [b], [C1C10Im][NTf2] [c].56, 59
74
Dupont et al. have already reported the preparation of NiNPs from Ni(COD)2 in
imidazolium based ILs in order to control the size of the NiNPs by varying the length of the
imidazolium alkyl substituent.56, 59
Here, the size of the NPs formed was found not to vary
greatly on changing the nature of the ionic liquid employed, i.e the alkyl side chain length, and in
contrast to previous findings from our group for RuNPs,26 the average size of NiNPs was found
to vary inversely with alkyl chain length, Figure 13. However, it is worth noting that a
substantial amount of benzene was used to aid the dissolution of Ni(COD)2 (6 mL of benzene for
2 mL of IL) and although effort was made to remove the volatiles before decomposition, we
cannot be sure of the complete removal of benzene and therefore the media in which the
decomposition actually occurred. Furthermore, the Ni-NiO core-shell particles produced bring
into question the purity of the solvents used. Therefore, the results are not comparable with the
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work in our laboratory, where pure neat ILs are used as the solvent.
2.3.1 Size-controlled synthesis of NiNPs
The synthesis of nickel nanoparticles, NiNPs, from the decomposition of bis-(1,5-
cyclooctadiene) nickel (Ni(COD)2), under molecular hydrogen (4 bars) at 0 °C or 25 °C, was
attempted firstly in the following imidazolium based ionic liquids (ILs); [C1CnIm][NTf2], with
n = 2, 4, 6, 8, 10, varying the length of the alkyl chain in order to investigate the effect on the
size of the resulting NiNPs.
2.3.1.1 Decomposition in [C1C6Im][NTf2], [C1C8Im][NTf2] and [C1C10Im][NTf2]
Firstly, Ni(COD)2 (50 mg, 0.14 mmol) was stirred into the ionic liquid (10 mL) until a
light yellow solution resulted (14 mmol L-1 in each case). For all three ILs, the solutions were
exposed to H2 (4 bar) at 0 °C or 25 °C producing after 3 days black suspensions of NiNPs,
Scheme 6, except in the case of [C1C6Im][NTf2] at 0 °C, where the reaction proceeded very
slowly, and the starting product was still present with the NPs. The resulting volatiles were
removed in vacuo, trapped and characterised by 1H and 13
C NMR spectroscopy. The spectra
obtained showed the predominance of cyclooctane, with a small amount of remnant 1,5-COD
and even a trace amount of its isomer 1,3-COD. We may conclude that in this case the
decomposition occurs mainly via the hydrogenation of 1,5-COD, and the small amount
unchanged ligand may undergo isomerisation in the presence of Ni-H.
75
H2 (4bar), 25 °C
NiNPs +
Ni
C1C4<nIm NTf2
Scheme 6. Decomposition of Ni(COD) under H2 – Route to obtain NiNPs
2.3.1.2 Effect of temperature

In [C1C8Im][NTf2] and [C1C10Im][NTf2] the NiNPs formed at 0 °C are smaller than those
generated at 25 °C, Figure 14.
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70
60
60
50 C8C1Im NTf2 0C
C8C1Im NTf2 RT 50
40
C10C1Im NTf2 0C
frequency
frequency
40
C10C1Im NTf2 RT
30
30
20
20
10 10
0 0
0 2 4 6 8 10 12 2 4 6 8 10 12
size / nm size/nm
Figure 14. Size distribution histrograms of NiNPs synthesized in [C1C8Im][NTf2] (left),and [C1C10Im][NTf2](right),
under 4 bars of H2 in various at 0 °C and at 25 °C
Even if the variation of H2 solubility as a function of the temperature is still under

discussion, the ILs are more viscous at 0 °C than at 25 °C, thus the H2 diffusion and its solubility
expected to be lower. Consequently, by working at 0 °C without stirring, the conditions
disfavoured hydrogen solubility and diffusion. This is different to that described by Aiken et al.,
who observed in similar conditions in organic solvent, the formation of irregular and aggregated
clusters.60 Moreover, in organic media, increasing temperature is often leads to a decrease in NP
size, due to the kinetics of the NP growth process.61, 62 Consequently, the differences observed in
ILs could once again be rationalised on the basis of their degree of self-organisation.25
76
2.3.1.3 Influence of the length of the alkyl side chains

When realised at the same temperature in different ILs [C1C6Im][NTf2], [C1C8Im][NTf2],
and [C1C10Im][NTf2] the decomposition of Ni(COD)2 resulted in different sized NPs as can be
seen in the histograms presented in Figure 15.
70
70
60
60
50
C6C1Im NTf2
50 C8C1Im NTf2 0C C8C1Im NTf2
C10C1Im NTf2 0C C10C1Im NTf2
frequency
40
frequency
40
30
30
20
20
10 10
0
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0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
size/ nm size/ nm
Figure 15. Size distribution histograms of NiNPs size synthesised under 4 bars of H2, at 0° and 25°C without
stirring in different ILs.
At room temperature, the observed mean diameter increases with the side alkyl chain
length: in [C1C6Im][NTf2], (5 ± 2 nm), in [C1C8Im][NTf2] (6 ± 2 nm). and in [C1C10Im][NTf2],
(7 ± 2 nm). It was noted that a "mirror" appeared on the bottom of the glass auto-clave during the
reaction in [C1C10Im][NTf2] at 25°C corresponding to the deposition of bulk metallic nickel.
2.3.1.4 Comparison with RuNPs
The synthesis of NiNPs under H2 in these ILs, was seen to give similar trends to RuNPs,
i.e. mean size of resultant NPs increasing with both increasing temperature and increasing alkyl
chain length. In the case of RuNPs, when n = 10 we observe the formation of large “sponge-like
superstructures” with a size of 100–150 nm containing small aggregated particles. This
phenomenon could result from a diffusive process of RuNPs between the different non-polar
domains due to the chain length. For NiNPs, this phenomenon is not observed, although at 25 °C
in the same IL, the deposition of a metallic mirror as well as the formation of NiNPs was
recorded.
Unlike RuNPs generated in situ the sizes of NiNP obtained were large, and with a
relatively broad size distribution. Indeed, the NiNPs obtained are too large to be correlated to the
measured size of the non-polar domains. The fact that they cannot be contained within these
77
domains may explain their gradual agglomeration and precipitation, observed in each case
between 5 and 10 days after formation, and storage under inert atmosphere.
These differences between RuNPs and NiNPs could be related to a different mechanism
involved in generation. The complex Ru(COD)(COT) reacts readily with H2.63 Consequently, its
decomposition under H2 rapidly affords nuclides which subsequently coalescence to generate
small RuNPs of controlled size.
On the other hand, a higher energy barrier is involved in its decomposition of Ni(COD)2.
Consequently, the formation of nuclides is slow. Few nickel nuclides therefore coexist with a
great deal of Ni(COD)2. The nuclides induce the decomposition of Ni(COD)2 meaning that the
growth process in this case is much faster than the nucleation and therefore fewer larger NPs are
formed with less control, as illustrated in Scheme 7.
tel-00708600, version 1 - 15 Jun 2012
Scheme 7. The kinetics of nucleation and growth in the formation of nanoparticles.64
Similarly to RuNPs, when a solution of freshly prepared NiNPs was treated under
ethylene, in the absence of H2, ethane was detected in the atmosphere, indicating the presence of
hydrides on the nickel surface.30, 65 However, unlike RuNPs when heated and stirred under an
atmosphere of H2, NiNPs undergo rapid coalescence and precipitation. Recently, it has been
reported that the size of NiNPs formed by “dewetting” of Ni metal film drastically increases with
increasing H2 pressure. By analogy with Raney nickel, this result has been related by the authors
to the formation of a surface hydride leading to a modification of the surface free energy.66
2.3.2 Spontaneous decomposition on solvation
In the absence of hydrogen, in neat [C1C2Im][NTf2] and [C1C4Im][NTf2] at room
temperature, and in [C1C6Im][NTf2] at 40 °C, spontaneous decomposition of Ni(COD)2 occurred
on dissolution. TEM was performed on the resulting black solutions and revealed in each case a
mixture of NiNPs (< 10 nm) and sponge-like agglomerates of larger particles, Figure 16. It can
be seen from the TEM image that these sponge-like structures clearly consist of individual
78
particles. This is completely different from Dupont’s work,56 emphasising the important role that
a co-solvent such as benzene plays in the medium.
tel-00708600, version 1 - 15 Jun 2012
Figure 16. Sponge-like agglomerates of NiNPs formed by autodecomposition of Ni(COD) 2 in [C1C4Im][NTf2]
Note that 1H NMR spectroscopy and gas chromatography performed on the resulting
solution showed only a trace of cyclooctane COA, resulting from the hydrogenation 1,5-COD,
the by-product of decomposition reported in the literature.53 Instead, the presence of both 1,5-
cyclooctadiene and its isomer 1,3-cyclooctadiene (1,3-COD) was detected by both gas
chromatography and 1H and 13
C NMR spectroscopy. 1,3-COD must be a result of 1,5-COD
isomerisation, which could only take place at a metal centre in the presence of [Ni]-H bond,
Scheme 8.
79
Ni H Ni H
Ni H
Ni Ni
Ni H
Scheme 8. Mechanism for the isomeration of COD necessitating a Ni-H
With RuNPs, the presence of surface hydrides has been proven by hydrogenation of
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ethylene without the addition of H2 by a solution of RuNPs in IL, as shown in Scheme 9.67 We
repeated this experiment for the NiNP solutions formed by autodecomposition of Ni(COD)2 in
the media.
Scheme 9. Hydrogenation of ethylene over RuNPs without addition of H2, - evidence for surface hydrides.
After treatment under ethylene atmosphere (4 bars, 100 °C, 24 h) no ethane was detected
by GC as a result of ethylene hydrogenation, however significant amounts of butenes and
hexenes were detected, probably a result of oligomerisation of the ethylene.
The formation of an ethyl substituted IL [C1C2C4Im][NTf2] was also observed by NMR
spectroscopies; 1H shown in Figure 17, COSY, HETCOR and DOSY; and confirmed by
electrospray mass spectrometry, where cations at m/z = 139 and 167 were observed with similar
abundances, corresponding to [C1C4Im]+ and [C1C2C4Im]+, respectively. Note that a small
amount of the cation [C1C4C4Im]+ was also observed by mass spectrometry, m/z = 195, probably
a result of oligomerisation of ethylene to 1-butene before reaction with the imidazolium cycle.
80
C12
C11
C2' C6' C8'

C10'
N N C7' C9' C10-H
C5' C4'
C10’-H C9-H
C6’-H C8-H
C11-H
C9’-H
C2-H C8’-H
C4-H C5-H C7-H
C12-H C7’-H
C4’-H C5’-H C6-H
C2 C6 C8
C10
N N C7 C9 C10-H
C2-H C9-H
C4-H C6-H C7-H C8-H
C5-H C5 C4
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9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 ppm
Figure 17. 1H NMR spectrum of [C1C4Im][NTf2] containing NiNPs from auto-decomposition, before (lower) and
after (upper) treatment under ethylene.
The evidence gathered suggests that the observed decomposition could be due to the
cleavage of the very acidic C2-H bond and the consequent in situ generation of a nitrogen
heterocyclic carbene (NHC), as already reported in the case of Ir NP preparation in ILs3, 5, 13 and
with homogeneous complexes of Ni68, Pd,69, 70 and of Rh and Ir.71
Cavell et al. have proposed a scheme for the possible catalytic cycle for the
imidazolium/alkene coupling reaction where the organometallic starting material they studied
was Ni(OAc)2.72 The same phenomenon has also been observed in work by Lecocq et al. who
were investigating the oligomerisation behaviour of Ni in imidazolium ionic liquids.68
At this point it is impossible to determine whether the observed reactions (isomerisation
of 1,5-COD and formation of C1C2C4ImNTf2) occur on molecular or colloidal species. However,
these results do prove that the cleavage of the C2-H bond does occur during the spontaneous
decomposition on dissolution. The proposed mechanism of the reaction of imidazolium salts
with low valent M0 (M = Pd and Ni) hypothesises the formation of a molecular carbene-M-H
species,73, 74
as also proposed in the catalytic cycle for oligomerisation and formation of
trialkylimidazolium species in Scheme 10.
81
Ni(COD)2
NiNP IL
COD Bu
N N
Ni(0)(COD) NTf2
R
Bu
N N
NTf2
R = Et, Bu
N N H
II II
Ni (COD) Ni (COD)
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N N
NTf2 NTf2
Bu Bu
N
NiII(COD)
N
NTf2
Bu
Scheme 10. The proposed catalytic cycle for oligomerisation of ethylene and formation
of trialkylimidazolium species.
The presence of bis(imidazolylidene)nickel complexes [(NHC)2NiH]+ was also detected

by mass spectrometry, implying that a molecular intermediate is in fact present as proposed. This
may be as a transient species and could be the active species for the abovementioned reactions.
Similar bis-carbene iodide nickel complexes have already been prepared in imidazolium ILs and
isolated by Wasserscheid’s group.72 These were indeed found to be active in the dimerisation of
butene carried out in ILs, although no production of NiNPs was noted here, perhaps due to the
presence of the strongly coordinating iodides.
2.3.3 Avoiding carbene formation
Although the exact mechanism remains unclear, from our investigations it is certain that
the spontaneous decomposition of Ni(COD)2 on dissolution into the ionic liquids with short alkyl
82
chains, involves attack on the acidic C2-H. This may be inhibited in the longer chain ionic liquids
due to the greater distance between the imidazolium ring and the non-polar domains, where
Ni(COD)2 will dissolve preferentially. If we are to achieve the generation of small size-
controlled NiNPs, we must find a way of inhibiting this auto-decomposition in imidazolium ILs
with short chains. Several strategies were attempted in order to circumvent the problem.
Firstly, [C1C1C4Im][NTf2] which does not contain the most acidic C2–H proton was used
as the solvent. Surprisingly, the Ni(COD)2 still decomposed on stirring, but this time afforded
well dispersed NiNPs (7 ± 2 nm), Figure 18. This can only be explained by attack on the two less
acidic protons C4-H,C5-H of the imidazolium ring and generation of transitory non-classical
NHC ligands.75
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30
25
C4C1C1Im NTf2
20
7 ± 2 nm
frequency
15
10
0
2 4 6 8 10 12
size/ nm
Figure 18. TEM image of NiNPs formed by autodecomposition of Ni(COD) 2 in [C1C1C4Im][NTf2] and size
distribution histogram.
Another possible solution to this spontaneous decomposition is to increase the strength of

the H-bond between C2-H on the cation and the anion. The more strongly co-ordinating anion
BF4- was selected, yielding important results. The formation of NiNPs in [C1C4Im][BF4]
occurred not spontaneously, but very slowly at 25 °C only under 4 bars of H2. The solution had
turned entirely black after 5 days. Analysis by TEM revealed well dispersed small NiNPs of
2.8 ±0.9 nm, Figure 19.
83
40
30 BF4 RT
Frequency
20
10
0
1 2 3 4 5 6 7
Size / nm
Figure 19. TEM image of NiNPs formed by decomposition of Ni(COD)2 under H2 (4 bars at 25 °C) in
[C1C4Im][BF4] and size distribution histogram.
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2.3.4 Conclusion
The synthesis of NiNPs from Ni(COD)2 under H2 (4 bar) has been carried out in various
imidazolium based ionic liquids at 0 °C and 25 °C. Imidazolium cations substituted with longer
chains [C1C6Im][NTf2], [C1C8Im][NTf2] and [C1C10Im][NTf2], the IL media were found to offer
fairly good media for the preparation and stabilisation of nickel nanoparticles. NiNP size
increased with increasing chain-length and in this way we were able to control NiNP size.
Additionally, upon decreasing the reaction temperature to 0 °C, we were able to produce smaller
NiNPs than those produced in the same IL media at 25 °C. The presence of surface hydrides on
on these NiNPs as on RuNPs has been evidenced by hydrogenation of ethylene in the absence of
hydrogen. The resulting NiNPs in these ILs were found to be larger than RuNPs produced in the
same media. This can be largely attributed to differences in the nucleation and growth processes
for the two metals.
Unexpectedly, spontaneous decomposition of Ni(COD)2 occurred without the addition of
hydrogen for imidazolium ILs with short alkyl chains; [C1C2Im][NTf2]. [C1C4Im][NTf2] and
[C1C1C4Im][NTf2]. In [C1C2Im][NTf2] and [C1C4Im][NTf2], TEM micrographs showed NiNPs
of fairly large diameter were formed as well as sponge-like super agglomerates. In
[C1C1C4Im][NTf2] well dispersed NiNPs are formed. In these cases, an explanation concerning
the activation of the acidic protons on the imidazolium ring and the consequent nitrogen
heterocyclic carbene formation leading to rapid decomposition of the complex, has been
proposed, Scheme 11.
84
Bu + Bu 1,3-COD
+ 2 (1,5-COD)
N N
N
A- N
Bu Me
C2
A- + Ni(1,5-COD)2 C2 [Ni] H N
H
Me
N
H 1,5-COD
Me
C2H4
?
Bu N + N N + N
Bu Me Bu Me
N C2 C2
+ H A- A-
C Et Bu
N 2 H
Me = Ni
Scheme 11. Reactions occuring during the autodecomposition of Ni(COD)2 in imidazolium ionic liquids.
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On changing the anion of the IL to the more strongly co-ordinating tetrafluoroborate

[C1C4Im][BF4], the acidic protons of the imidazolium ring were protected, and more controlled
NiNP formation took place, only in the presence of hydrogen. This medium was therefore
successfully used to synthesise NiNPs smaller than 4 nm in diameter.
This work provides a novel route to NiNP synthesis and offers the possibility of NiNPs in
ILs as a medium for catalysis.
85
2.4 Tantalum nanoparticles
To meet the constant challenge of miniaturisation in the microelectronics industry,

traditional methodologies must be replaced by new innovative pathways to produce nano-
objects. In particular, oxophilic metals of groups 4 to 6 are of great interest due to their various
applications, e.g. as conducting contacts between active devices,76 or as barriers to the diffusion
of metals such as Cu.77 These metals could be used as thin layers but also as nanoparticles, NPs,
thus exhibiting further interesting properties that increase their appeal, such as quantum effects
and heightened reactivity.78 Recently, the potential of NP suspensions in ILs for use in electronic
applications has been revealed.79, 80Among metals of group 4 to 6, tantalum is currently of large
importance with 79% of the world’s annual production being used in electronics.81
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Note that of the early transition metals, only chromium, molybdenum and tungsten NPs
in ILs are reported in literature. They are obtained by by thermal or photolytic decomposition
under argon of mononuclear metal carbonyl precursors M(CO)6 (M = Cr, Mo, W).82
The number of publications describing the synthesis of Ta(0)NPs, is limited. Due to high
melting and boiling points, Ta(0)NPs are difficult to prepare by conventional physical methods.
For example, the preparation of Ta(0)NPs by a hydrogen rich plasma (water used as the
plasmatic medium as it dissociates under the effect of an electric arc) led to a mixture of
Ta(0)NPs and TaO NPs.83 Studies by XRD indicate that the TaO NPs present a hexagonal phase
with interplanar distances of 0.31 and 0.39 nm depending on the face under study (100 and 001
respectively). The Ta(0)NPs however, have a face centred cubic structure much like bulk Ta
metal. Their average size was estimated to be 10 nm and interplanar distances of the (110) face
were measured as being 0.24 nm.84
Chemical methods are rarely used. They involve the reduction of TaCl5 or K2TaF7 at high
temperature or in liquid ammonia in the presence of sodium.85, 86 Such techniques result in Ta
particles of sizes ranging between 1 – 100 μm. More recently, Ta(0)NPs supported on silica have
been described. The reaction of pentabenzyl tantalum, Ta(CH2C6H5)5, with the silica surface,
results in the formation of surface complex(es) that under hydrogen atmosphere at 573 K and
723 K, lead to the formation of Ta(0)NPs on SiO2 Scheme 12.87 Such Ta(0)NPs, of mean size
1 nm, contain Ta-Ta bond lengths of 2.93 Å (determined by EXAFS) and Ta-O-Si bond
lengths of 1.9 Å. The latter would suggest that the Ta(0)NPs are chemically bonded to the
86
surface. The question of the oxidation state of these surface Ta(0)NPs remains unanswered,
having not yet obtained XPS data.
H2
Ta(CH2Ph)5 + Si O2 ( SiO)nTa(CH3Ph)5-n [SiO2][Ta(0)]
nPhCH3 alkanes,
aromatics
Scheme 12. The synthesis of silica supported TaNPs87
Although ILs are known to be good media for the synthesis and stabilisation of NPs, few
papers regarding oxophilic metals are available.82 To our knowledge, no Ta(0)NPs have yet been
synthesised in ionic liquid media, although several examples of the electroreduction of tantalum
halides are reported leading to electroplated Ta on Pt electrodes, without reduction of the ionic
liquids.88-90 Here, a thin layer of halides is present at the surface, outlining the consequences and
tel-00708600, version 1 - 15 Jun 2012
importance of the chosen starting complex.

As previously discussed; in both organic and IL media, it has been widely reported that
treatment of group VIII organometallics under H2 leads to zero-valent transition metal NPs at
moderate temperature. The alkanes produced are inert towards the surface of the M(0)NPs and
easily eliminated under vacuum.25, 91, 92 In the case of the oxophilic group early transition metals,
such a strategy is not evident as zero oxidation state complexes are few and far between. For this
reason, as for the preparation of supported TaNPs on silica,87 we propose the use of an
organometallic precursor of Ta(V) as a source of Ta(0)NPs, namely
tris(neopentyl)neopentylidene tantalum(V), Np3Ta=CHCMe3, 1, whose synthesis is well
documented.93
2.4.1 Synthesis in pure [C1C4Im][NTf2]
The synthesis of Ta(0)NPs in 1-butyl-3-methylimidazolium bis(trifluomethylsulphonyl)-
imide, [C1C4Im][NTf2] from Np3Ta=CHCMe3, 1, was performed as follows. 1 (25 mg, 5.4.10-5
mol) was dissolved in pure dried [C1C4Im][NTf2] (5 mL) by vigorous stirring under argon. The
mixture was transferred into a Fischer-Porter bottle via a canula, which was then charged with
4 bars of H2 during a period of 72 h at 25 °C. This afforded a black suspension which was stable
several days under argon at 25 °C. Analysis of the gas phase after reaction by gas
chromatography showed the presence of only neopentane. The Ta(0)NPs produced were
analysed by transmission electron microscopy, TEM, from which a size distribution histogram
(in number) was constructed (Figure. 20) giving a mean size of 5 ± 3 nm (c.a. 70 % of NPs).
87
However, the NPs were not monodisperse as larger species of up to ~ 18 nm were also detected
(c.a. 30 % of NPs larger than 10 nm).
35
30
25
Frequency
20
15
10
0
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0 2 4 6 8 10 12 14 16 18
Size/ nm
Figure 20. Size distribution histogram for TaNPs formed in [C1C4Im][NTf2]
2.4.2 Addition of a co-solvent

During the dissolution of 1 into [C1C4Im][NTf2], a problem of solubility was noted,
despite an extensive stirring period, probably the cause of the production of larger NPs outside of
the normal distribution. In the literature several groups have overcome such a problem by
addition of a co-solvent to aid the dissolution of the organometallic complex into the ionic
liquid.56,57 Therefore in subsequent experiments, 1 was first dissolved in toluene or in pentane
before addition to [C1C4Im][NTf2]. Before proceeding, it was first ascertained that a simple
organic solution of 1 did not lead to NPs under pressure of H2 without the IL present. A ratio of
organic solvent to [C1C4Im][NTf2] was used such that a maximum amount of 1 would dissolve,
and demixing would not occur, i.e. n-pentane/IL = 2 % and toluene/IL = 36 % (weight
percentages). 1 is highly soluble in n-pentane which is inactive towards the NP surface and
therefore easily eliminated. However, pentane is poorly soluble in [C1C4Im][NTf2]. 1 is less
soluble in toluene but toluene was chosen due to its relatively high solubility in [C1C4Im][NTf2].
Once prepared, these solutions were treated under H2 as before, and the NP solutions produced
were analysed by TEM, and the size distribution histograms constructed, Figure 21. The
resulting NP sizes are tabulated below, Table 1.
88
50
45
40
with toluene 36%
35
with pentane 2%
30 no co-solvent
Frequency 25
20
15
10
0
0 5 10 15
Size/ nm
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Figure 21. Superimposed size distribution histograms for TaNPs produced in [C1C4Im][NTf2] neat and in the
presence of co-solvents, pentane (2 % wt) and toluene (36 % wt).
Table 1. Resulting sizes of TaNPs, produced in different media under H 2 (4 bars) and 25 °C
Ionic Liquid Co-solvent Mean size NPs (nm)
C1C4Im NTf2 none 5 ± 3 (70%) (<10 (30%))
C1C4Im NTf2 toluene (36% wt) 5±3
C1C4Im NTf2 n-pentane (2% wt) 5±1
Due to the structured nature of ionic liquids, previously determined by molecular

dynamics simulations, non-polar substrates are contained within non-polar pockets of the IL,
created by the alkyl chains causing a swelling of these pockets.16 It has also been reported that
these domains are responsible for the size control of certain NPs generated in ILs.26 It is evident
that increasing the size of these domains by addition of a non-polar solvent increases the
solubility of 1 in [C1C4Im][NTf2], and thus the size distribution is largely monodisperse. This is
especially clear for the addition of a small amount of pentane, Figure 21.
However, the NP mean size remains large with respect to RuNPs generated in
[C1C4Im][NTf2], in the absence of solvent. As the addition of a non-polar solvent causes a
swelling of these domains, the larger size of Ta(0)NPs compared to RuNPs may be explained,
although it could be due to a different growth and stabilisation mechanism, as observed in the
case of nickel.
89
2.4.3 Increasing the chain length

In imidazolium ILs, for a given anion, the solubility of a nonpolar substrate increases
upon increasing the length of the alkyl chain.94 Consequently, another means of increasing the
solubility of 1 would to be to increase the length of the alkyl chain on the imidazolium of the IL.
A second approach was therefore employed involving the use of the hexyl- substituted ionic
liquid [C1C6Im][NTf2]. Here, 1 was fully dissolved into pure dried [C1C6Im][NTf2] without co-
solvent and the decomposition proceeded as previously described. In this medium smaller NPs
were produced, 3 ± 1 nm, with a narrower size distribution, Figure 22. The decrease in size
compared to [C1C4Im][NTf2], is contradictory to observations for RuNPs.26 This could be
explained by the decreased polarity of this medium and much enhanced solubility of the
precursor. Indeed, in the generation RuNPs we observe a similar phenomenon when changing
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from [C1C2Im][NTf2] to [C1C4Im][NTf2] attributed to the higher polarity of the former.26
80
60
Frequency
C1C6Im NTf2
C1C4Im NTf2
40
20
0
0 2 4 6 8 10 12 14 16 18
Size/ nm
Figure 22. Comparative size distribution histograms of TaNPs produced in [C1C4Im][NTf2] and [C1C6Im][NTf2]
and TEM image of those formed in the latter.
2.4.4 High resolution electron microscopy of TaNPs

A sample of TaNPs produced in [C1C4Im][NTf2] has also been analysed by high
resolution electron microscopy, HREM, in the absence of air. From the images obtained,
interplanar distances within the nanoparticles were found to be of 2.2Ǻ corresponding to the
(110) face of bulk fcc crystalline tantalum metal, Figure 23.84 This provides significant evidence
to suggest the particles generated are of tantalum in its zero oxidation state and not oxidised
forms. Given the high oxophilicity of Ta metal however, these NPs must be kept under an inert
90
atmosphere to remain zero-valent. The NP suspensions produced were not stable and decanted
over time. This presents the possibility of facile extraction of the NPs produced for use in other
media.
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Figure 23. HREM images of crystalline TaNPs produced in [C1C4Im][NTf2]. Interplanar distances indicated by the
arrows are of 2.2 Å.
2.4.5 Conclusion
In conclusion, we have demonstrated that small monodisperse and zero-valent tantalum
nanoparticles, Ta(0)NPs, may be generated under mild conditions, by decomposition of the
organometallic complex tris(neopentyl)neopentylidene tantalum(V), under H2 in imidazolium
derived ionic liquids. The control of the size and the factors of stabilisation of these NPs in ionic
liquids are currently under investigation. This method has opened up the possibility of facile
access to other oxophilic metal nanoparticles, which we are currently studying, and could be of
great potential interest in the drive for smaller and more efficient electronic devices.
91
2.5 Experimental Section
2.5.1 Materials and Methods

All operations were performed in the strict absence of oxygen and water under a purified
argon atmosphere using glovebox (Jacomex or MBraun) or vacuum-line techniques.
Ionic Liquid syntheses
The synthesis of [C1C4Im][NTf2] is reported below. All other syntheses imidazolium
ionic liquids [C1C6Im][NTf2], [C1C8Im][NTf2], [C1C10Im][NTf2], [C1C4//Im][NTf2],
[C1BzIm][NTf2], were synthesised in the same way, as reported.69
1-butyl-3-methylimidazolium chloride [C1C4Im][Cl] 1-chlorobutane (106 mL, 1.01 mol)
was added to freshly distilled 1-methylimidazole (50 mL, 0.63 mol). The mixture was stirred for
tel-00708600, version 1 - 15 Jun 2012
48 h at 65 °C. The hot solution was then transferred dropwise via a canula into toluene (200mL)
at 0 °C under vigorous mechanical stirring. The white precipitate formed was then filtered and
washed repeatedly with toluene (3 × 200 mL) and dried over night in vacuo giving a white
powder (95.6 g, 87 %). 1H-NMR (CD2Cl2): δ (ppm) : 11.05 (s, 1H, C2H) ; 7.33 (d, 1H, C4H) ;
7.28 (d, 1H, C5H) ; 4.31 (t, 2H, NCH2) ; 4.07 (s, 3H, NCH3) ; 1.90 (qt, 2H, CH2CH2CH2) ; 1.41
(st, 2H, CH2CH2CH3) ; 0.96 (t, 3H, CH2CH3) ; 13C{1H}-NMR (CD2Cl2) : δ (ppm) : 138.3 (C2H) ;
122.3 (C4H) ; 119.8 (C5H) ; 50.1 (NCH2) ; 36.8 (NCH3) ; 32.5 (CH2CH2CH2) ; 19.8
(CH2CH2CH3) ; 13.6 (CH2CH3)
1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide [C1C4Im][NTf2] A
solution of lithium bis(trifluorosulphonylimide) [LiNTf2] (50 g, 0.17 mol) in water (50 mL) was
added to a solution of BMICl (30.4 g, 0.17 mol) in water (100 mL). The solution was stirred for
2 h at room temperature, then dichloromethane (50 mL) was added and the mixture transferred to
a separating funnel. The lower phase was collected and washed repeatedly with water
(8 × 100 mL) until no chloride traces remained in the washings (tested with silver nitrate
solution). The ionic liquid in dichloromethane was purified through a short alumina column and
the solvent removed in vacuo giving a colourless viscous liquid. 1H-NMR (CD2Cl2): δ (ppm) :
8.73 (s, 1H, C2H) ; 7.28 (d, 1H, C4H) ; 7.24 (d, 1H, C5H) ; 4.15 (t, 2H, NCH2) ; 3.90 (s, 3H,
NCH3) ; 1.83 (qt, 2H, CH2CH2CH2) ; 1.32 (st, 2H, CH2CH2CH3) ; 0.94 (t, 3H, CH2CH3) ;
13
C{1H}-NMR (CD2Cl2) : δ (ppm) : 134.3 (C2H) ; 124.3 (C4H) ; 122.4 (C5H) ; 118.2 (CF3) ; 50.3
(NCH2) ; 37.1 (NCH3) ; 33.2 (CH2CH2CH2) ; 19.8 (CH2CH2CH3) ; 13.5 (CH2CH3)
92
1-Methylimidazole (> 99 %) was purchased from Aldrich and distilled prior to use.
Chlorobutane, benzyl chloride and 4-chlorobut-1-ene (> 99 %, Aldrich) were used without
further purification. Bis(trifluoromethanesuflonyl)imide lithium salt (> 99 %, Solvionic) was
used without further purification.
Organometallic complexes
( 4-1,5-cyclooctadiene)(
)( 6-1,3,5-cyclooctatriene)ruthenium(0) Ru(COD)(COT) was
95
synthesised as reported. Degassed cycloocta-1,5-diene (60 mL, 0.49 mol) filtered over alumina
and zinc dust (10.0 g) were added to a solution of RuC13.3H2O (3.6 g, 13.7 mmol) in distilled
degassed methanol (50 mL). The mixture was heated under reflux with magnetic stirring for 6 h
and then filtered, washing the solid residue with dry degassed toluene. The resulting brown
solution was evaporated in vacuo until the residue was completely dry. Extraction with n-pentane
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(2 mL) gave a red solution which was filtered through a column of alumina (20 cm), resulting in
a yellow solution. The volume of the solvent was reduced to ca. 5 mL in vacuo and the yellow
solution was cooled to - 78 °C to give, in 6 h, yellow crystals of Ru(COD)(COT) (1.7 g, 43 %),
m.p. 92 - 94 °C. 1H-NMR (C6D6) δ (ppm) : 4.78 (dd, 2 H), 5.22 (m, 2 H), 6.21 (m, 2 H), 7.08 (m,
4 H), 7.78 (m, 8 H), 8.36 (m, 2 H), 9.10 (m, 2 H).
s( 4-1,5-cyclooctadiene)nickel(0), Ni(COD)2, (Strem > 99 %) was used as recieved.
Bis(
Tris(neopentyl)(neopentylidene)tantalum(V), Ta Schrock, was prepared according to the
literature procedure. 93 A 1.56 M solution of NpMgCl in diethylether (100 mL) was added drop-
wise over 0.5 h to a stirred suspension of TaCl5 (6.0 g, 16 mmol) in 150 mL of diethylether at
room temperature. Any solid TaC15 rapidly dissolved as the reaction proceeded through stages
characterized by greenish-yellow, yellow, and finally, orange-brown colours. The final solution
contained some magnesium chloride, which was removed by filtration over celite. All solvent
was removed in vacuo and the residue sublimed in two stages at 90 °C and ~ 10-8 bar to give
1.7 g (22 %) of deep orange crystals on the probe. 1H-NMR (C6D6) δ (ppm): 8.09 (s, 1H) , 8.57
(s, 9H), 8.85 (s, 27H), 9.16 (s, 6H)
Nanoparticles
Ruthenium In a typical synthesis, Ru(COD)(COT) (66 mg, 0.21 mmol) was stirred
virorously into the dry degassed ionic liquid (5 mL). The resulting bright yellow suspension was
then transferred via canula to a Fischer-Porter bottle, in a thermostatic bath (0° C or 25° C),
which was pressurised under pure H2 or D2 (4 bars) over 3 days (0° C) or 18 h (25° C). The
93
volatiles (cyclooctane) were subsequently removed under reduced pressure and the resultant
black solution was stored under inert (Ar) atmosphere in the glovebox.
Nickel – decomposition under H2.The same procedure as above was applied to Ni(COD)2
(50 mg, 0.14 mmol) in ionic liquid [C1Cn>4Im][NTf2] (10 mL).
Nickel – decomposition on dissolution. Ni(COD)2 (50 mg, 0.14 mmol) was stirred into
ionic liquid [C1Cn≤4Im][NTf2] (10 mL) producing a pale yellow solution at 25 °C. After 1 h the
solution had turned green and after a further hour the solution a black solution resulted.
Tantalum. Ta Schrock (25 mg, 5.4×10-5 mol) was dissolved in the ionic liquid (10 mL) or
ionic liquid-organic solvent mixture (dry, degassed toluene or pentane). The resulting orange
solution was canulated into a Fischer-Porter bottle, which was pressurised under 4 bars of H2 at
25 °C during 4 days. A black solution resulted, which was stored in a glove box under argon.
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2.5.2 NMR Spectroscopy

Solution NMR spectra were recorded on Bruker Avance 300 MHz spectrometer for 1H
and 13C. DRX 500MHz for 2H. Gas phase 1H NMR spectra were obtained on a Bruker DRX 500
instrument at 298 K (nominal) with a resonance frequency at 500 130 MHz.
2.5.3 Mass spectrometry
Mass spectra were acquired on a ThermoFinnigan LCQ Advantage ion trap instrument,
detecting positive (+) an negative ( ) ions in the ESI mode. Samples (1 to 10 µg/mL in
acetonitrile) were infused directly into the source (5 µL.min-1) using a syringe pump. The
following source parameters were applied: spray voltage 3.0 3.5 kV, nitrogen sheath gas flow
5 20 arbitrary units. The heated capillary was held at 200°C. MS spectra were obtained by
applying a relative collision energy of 25 to 40% of the instrumental maximum.
1) ESI+ mass spectrum for [C1C4//Im][NTf2] after deuterium incorporation.
[C1C4//Im][NTf2]:
94
137.1
100
90
80
70
60
50
40
30
138.1
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20
141.1
140.1
10
139.1 142.1
143.1 144.2 145.2 146.2 147.2
0
138 139 140 141 142 143 144 145 146 147
m/z
Relative peak intensities from the above spectrum
2) ESI+ mass spectrum for [C1BzIm][NTf2] after deuterium incorporation
[C1BzIm][NTf2]:
95
LCQ081023-02 #143-245 RT: 2.36-2.89 AV: 103 NL: 9.98E7

T: + c ESI Full ms [ 150.00-180.00]
173.1
100
90
80
70
60
50
40
174.1
30
20
10 175.1
171.1 171.7 176.2 177.2 178.2

0
171 172 173 174 175 176 177 178
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m/z
ESI+ spectrum – deuterated methylenecyclohexyl region
LCQ081023-02 #674 RT: 8.03 AV: 1 NL: 1.77E5

T: + p ESI Z ms [ 175.00-195.00]
185.2
100
175.2
90
80 186.2
184.2
70
60
183.2
50 187.2
181.2
182.2
40
188.2
30
180.2
176.1
20 189.2
179.2
190.2
10 178.0 191.2 193.2 193.8 194.4
177.1
0
176 178 180 182 184 186 188 190 192 194
m/z
96
2.5.4 Transition Electron Microscopy

Samples for TEM observations were prepared by placing a thin film of the nanoparticles
dispersed in ionic liquids on a copper grid coated with holey carbon film. The size distribution
histograms of the metal particles were constructed from the measurement of roughly 200
particles, assuming spherical shape.
The transmission electronic microscopy (TEM) experiments were performed directly in
the IL media. A thin film of RuNP solution in IL was deposited on a carbon film supported by a
copper grid. Conventional TEM micrographs were obtained at the “Centre Technologique des
Microstructures”, UCBL1, Villeurbanne, France, using a Philips 120 CX electron microscope.
The acceleration voltage was 120 kV. Size distribution histograms were constructed from the
measurement of at least 200 different nanoparticles assuming a near spherical shape and random
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orientation.
2.5.5 GC analyses
The products were quantitatively analysed by gas chromatography on a P6890
chromatograph equipped with a flame ionisation detector (FID) and an Al2O3/KCl column (L )
50 m, φint ) 0.32 mm, film thickness ) 5 μm). The injector and detector temperature was 230° C,
and the injection volume was 1 μL. The temperature was fixed at 190° C.
2.5.6 Hydrogenation of Ethylene by RuNPs in the IL
A 2 mL sample of the RuNP solution in the IL was introduced under argon into a Schlenk
of known volume. The sample was treated under flow of argon for 18 h. The argon atmosphere
was replaced with a known pressure of ethylene using a vacuum line and the system was stirred.
A decrease of the internal pressure was observed, and the composition of the gas phase was
monitored by gas chromatography. After 12 h, the atmosphere was replaced by a H2 atmosphere
and the system was heated and stirred for 12 h. The composition of the gas phase was again
monitored by gas chromatography.
Ethylene Hydrogenation Calculations
pV = nRT
Vreactor = 125.8 cm3 = 1.258 × 10-4 m3
pr = 129 mbar = 1.2 × 104 Pa
R = 8.314 m3 Pa K-1 mol-1
T = 298 K
97
n = (1.29 ×104 ×1.258 ×10-4) / (8.314 × 298) m3 Pa m-3 Pa-1 K mol K-1 =
6.54 × 10-5 mol ethylene introduced
GC calibration results: 2.3×10-12 × A = no. moles of C
300µL injections = 3×10-7 m3
Table 2. GC results following treatment under ethylene
Species Ret time/ mins Peak Area No. Moles of C No. of Moles (in No. of Moles (in
300 µL) reactor)
ethane 4.816 2.31×104 5.3×10-8 2.7×10-8 1.1×10-5
ethylene 5.094 6.57×104 1.5×10-7 7.6×10-8 3.2×10-5
isobutane 8.322 367 8.4×10-10 2.1×10-10 8.8×10-8
butenes 10.5 805 1.9×10-9 4.6×10-10 1.9×10-7

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C2H4 + H2 à C2H6:
1 mole ethane produced = 1 mole H2 consumed, i.e. 2 moles of surface hydrides
2C2H4 + H2 à C4H10:
1 mole isobutane produced = 1 mole H2 consumed, i.e. 2 moles of surface hydrides
2C2H4 à C2H8
1 mole butene produced = No H2 consumed
Table 3. GC results following treatment under H2 liberating surface alkyls
Species Ret time/ mins Peak Area No. Moles of C No. of Moles (in No. of Moles (in
300 µL) reactor)
methane 4.501 4.79×103 1.1 ×10-8 1.1 ×10-8 4.6 ×10-6
ethane 4.826 1.69×104 3.9 ×10-8 1.9 ×10-8 8.1 ×10-6
n-propane 5.871 8.47×103 1.9 ×10-8 6.5 ×10-9 2.7 ×10-6
n-butane 8.753 4.04×103 9.2×10-9 2.3 ×10-9 9.7 ×10-7
n-pentane 12.434 463 1.1×10-9 2.1 ×10-10 8.9 ×10-8
½ C2H4 + ½ H2 à -CH3
1 mole methyl produced = ½ mole H2 consumed, i.e. 1 mole of surface hydrides
C2H4 + ½ H2 à -C2H5
1 mole ethyl produced = ½ mole H2 consumed, i.e. 1 mole of surface hydrides
1½ C2H4 + ½ H2 à -C3H7
98
1 mole propyl produced = ½ mole H2 consumed, i.e. 1 mole of surface hydrides

2C2H4 + ½ H2 à -C4H9
1 mole butyl produced = ½ mole H2 consumed, i.e. 1 mole of surface hydrides
2½ C2H4 + ½ H2 à -C5H11
1 mole pentyl produced = ½ mole H2 consumed, i.e. 1 mole of surface hydrides
Total surface hydrides counted = 38 µmol
Ethylene Mass balance
6.54 ×10-5 mol (introduced) - 6.02×10-5 mol (detected by GC) = 5.2 µmol ~ 8 % error
2.5.7 H-D exchange
A 2mL sample of the RuNP solution in the IL was introduced under argon into a Schlenk,
which was then treated under dynamic vacuum (10-5 mbar) during a period of 1h or 4h. This was
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then charged with deuterium (1 bar) and stirred at 25°C during a period of 1 or 4 days. The gas
phase was subsequently expanded into an airtight Young tube for NMR analysis.
2.5.8 TON calculations
Butenyl IL à butyl IL
Ru(COT)(COD) – 2.2 × 10-4 moles
RuNPs, 1.1 ± 0.2 nm, dispersion ~75%
Rus – 1.7 × 10-4 moles
Butenyl IL 7.5g/ 417g mol-1 = 1.8 × 10-2 moles
15 % converted à 2.7 × 10-3 moles
TON à 2.7 × 10-3 moles/ 1.7 × 10-4 moles = 16
Benzyl IL à methylenecyclohexyl IL
Ru(COT)(COD) – 2.2 × 10-4 moles
RuNPs, 3.2 ± 0.7 nm, dispersion ~35%
Rus – 7.7 × 10-5 moles
Benzyl IL 7.5g/ 453g mol-1 = 1.7 × 10-2 moles
30% converted à 4.9 × 10-3 moles
TON à 4.9 × 10-3 moles/7.7 × 10-5 moles = 64
99
2.6 References

2. A. Corma, I. Dominguez, T. Rodenas and M. J. Sabater, J. Catal., 2008, 259, 26-35.
3. L. S. Ott and R. G. Finke, Coord. Chem. Rev., 2007, 251, 1075-1100.
4. A. P. Umpierre, G. Machado, G. H. Fecher, J. Morais and J. Dupont, Adv. Synth. Catal.,
2005, 347, 1404-1412.
5. L. S. Ott and R. G. Finke, Inorg. Chem., 2006, 45, 8382-8393.
6. H. Bönnemann, K. S. Nagabhushana and R. M. Richards, in Nanoparticles and Catalysis,
ed. D. Astruc, Wiley-VCH, Weinheim, 2008.
7. J. Dupont and D. De Oliveira Silva, in Nanoparticle Catalysis, ed. D. Astruc, Wiley-
tel-00708600, version 1 - 15 Jun 2012
VCH, Weinheim, 2008.

8. S. Oezkar and R. G. Finke, J. Am. Chem. Soc., 2002, 124, 5796-5810.
9. G. S. Fonseca, G. Machado, S. R. Teixeira, G. H. Fecher, J. Morais, M. C. M. Alves and
J. Dupont, J. Colloid Interface Sci., 2006, 301, 193-204.
11. H. S. Schrekker, M. A. Gelesky, M. P. Stracke, C. M. L. Schrekker, G. Machado, S. R.
Teixeira, J. C. Rubim and J. Dupont, J. Colloid Interface Sci., 2007, 316, 189-195.
12. L. S. Ott, S. Campbell, R. Seddon Kenneth and G. Finke Richard, Inorg. Chem., 2007,
46, 10335-10344.
13. L. S. Ott, M. L. Cline, M. Deetlefs, K. R. Seddon and R. G. Finke, J. Am. Chem. Soc.,
2005, 127, 5758-5759.
14. J. N. A. Canongia Lopes and A. A. H. Padua, J. Phys. Chem. B, 2006, 110, 3330-3335.
15. A. Triolo, O. Russina, H.-J. Bleif and E. Di Cola, J. Phys. Chem. B, 2007, 111, 4641-
4644.
40, 1087-1096.
17. M. G. Del Popolo, C. L. Mullan, J. D. Holbrey, C. Hardacre and P. Ballone, J. Am. Chem.
Soc., 2008, 130, 7032-7041.
18. M. Antonietti, D. Kuang, B. Smarsly and Y. Zhou, Angew. Chem. Int. Ed., 2004, 43,
4988-4992.
100
19. E. R. Cooper, C. D. Andrews, P. S. Wheatley, P. B. Webb, P. Wormald and R. E. Morris,

Nature, 2004, 430, 1012-1016.
110, 16816-16818.
21. L. M. Rossi and G. Machado, J. Mol. Catal. A, 2009, 298, 69-73.
22. C. Pan, K. Pelzer, K. Philippot, B. Chaudret, F. Dassenoy, P. Lecante and M.-J.
Casanove, J. Am. Chem. Soc., 2001, 123, 7584-7593.
23. K. Pelzer, K. Philippot and B. Chaudret, Z. Phys. Chem., 2003, 217, 1539-1547.
3740.
tel-00708600, version 1 - 15 Jun 2012

27. K. Philippot and B. Chaudret, C. R. Chimie, 2003, 6, 1019-1034.
28. T. Pery, K. Pelzer, G. Buntkowsky, K. Philippot, H.-H. Limbach and B. Chaudret,
ChemPhysChem, 2005, 6, 605-607.
29. J. Garcia-Anton, M. R. Axet, S. Jansat, K. Philippot, B. Chaudret, T. Pery, G.
Buntkowsky and H.-H. Limbach, Angew. Chem. Int. Ed., 2008, 47, 2074-2078.
30. J. R. Anderson, Structure of metallic Catalysts, Acadamic Press, London, 1975.
31. R. Berthoud, P. Delichere, D. Gajan, W. Lukens, K. Pelzer, J.-M. Basset, J.-P. Candy and
C. Coperet, J. Catal., 2008, 260, 387-391.
32. J. Okal, Catal. Commun., 2010, 11, 508-512.
33. M.-C. Daniel and D. Astruc, Chem. Rev., 2004, 104 293-346.
34. J. L. Anthony, J. L. Anderson, E. J. Maginn and J. F. Brennecke, J. Phys. Chem. B, 2005,
109, 6366-6374.
35. R. Van Hardeveld and F. Hartog, Surf. Sci., 1969, 15, 189-230.
36. J.-M. Basset et al., in Modern Surface Organometallic Chemistry, ed. J. M. Basset, Psaro
Rinaldo, Roberto Dominique, Ugo Renato, Wiley VCH, Weinheim, 2009, pp. 23-68.
37. M. Leconte, A. Theolier and J. M. Basset, J. Mol. Catal. A, 1985, 28, 217-231.
101
38. M. Leconte, A. Theolier, D. Rojas and J. M. Basset, J. Am. Chem. Soc., 1984, 106, 1141-
1142.
39. I. M. Ciobica, A. W. Kleyn and R. A. Van Santen, J. Phys. Chem. B 2003, 107, 164-172.
40. T. H. Rod, A. Logadottir and J. K. Norskov, J. Chem. Phys., 2000, 112, 5343–5347.
41. J. Wang, C. Y. Fan, Q. Sun, K. Reuter, K. Jacobi, M. Scheffler and G. Ertl, Angew.
Chem. Int. Ed., 2003, 42, 2151-2154.
42. M. P. Stracke, M. V. Migliorini, E. Lissner, H. S. Schrekker, D. Back, E. S. Lang, J.
Dupont and R. S. Goncalves, New J. Chem., 2009, 33, 82-87.
43. A. Roucoux, A. Nowicki and K. Philippot, in Nanoparticles, ed. D. Astruc, Wiley-VCH,
Weinheim, 2007, p. 351.
44. L. Cammarata, S. G. Kazarian, P. A. Salter and T. Welton, Phys. Chem. Chem. Phys.,
tel-00708600, version 1 - 15 Jun 2012
2001, 3, 5192-5200.
45. Y.-Y. Jiang, Z. Zhou, Z. Jiao, L. Li, Y.-T. Wu and Z.-B. Zhang, J. Phys. Chem. B, 2007,
111, 5058-5061.
46. A. Mele, C. D. Tran and S. H. De Paoli Lacerda, Angew. Chem. Int. Ed., 2003, 42, 4364-
4366.
47. A.-L. Rollet, P. Porion, M. Vaultier, I. Billard, M. Deschamps, C. Bessada and L.
Jouvensal, J. Phys. Chem. B, , 2007, 111 11888 -11891.
48. B. L. Bhargava and M. L. Klein, J. Phys. Chem. B, 2009, 113, 9499-9505.
49. B. L. Bhargava and M. L. Klein, Soft Matter, 2009, 5, 3475-3480.
50. S. Pickering, J. Chem. Soc., 1907, 91, 307.
51. L. Lu, M. L. Sui and K. Lu, Science, 2000, 287, 1436.
52. H. Wang, X. Jiao and D. Chen, J. Phys. Chem. C, 2008, 112, 18793-18797.
53. N. Cordente, C. Amiens, B. Chaudret, M. Respaud, F. Senocq and M.-J. Casanove, J.
Appl. Phys. , 2003, 94, 6358-6365.
54. N. Cordente, M. Respaud, F. Senocq, M.-J. Casanove, C. Amiens and B. Chaudret, Nano
Lett., 2001, 1, 565-568.
55. T. Ould Ely, C. Amiens and B. Chaudret, Chem. Mater., 1999, 11, 526-529.
56. P. Migowski, G. Machado, S. R. Texeira, M. C. M. Alves, J. Morais, A. Traverse and J.
Dupont, Phys. Chem. Chem. Phys., 2007, 9, 4814-4821.
102
57. P. Migowski, S. R. Teixeira, G. Machado, M. C. M. Alves, J. Geshev and J. Dupont, J.

Electron Spectrosc., 2007, 156-158, 195-199.
58. T. N. Rostovshchikova, Catal. Today, 2005, 105, 344-349.
59. P. Migowski and J. Dupont, Chem.--Eur. J., 2007, 13, 32-39.
60. I. Aiken, J. D., and R. G. Finke, J. Am. Chem. Soc., 1998, 120, 9545-9554.
61. K. Pelzer, O. Vidoni, K. Philippot, B. Chaudret and V. Collière, Adv. Funct. Mater.,
2003, 13, 118-126.
62. R. G. Finke, Coord. Chem. Rev., 2007, 251, 1075–1100.
63. P. Pertici, G. Simonelli, G. Vitulli, G. Deganello, P. Sandrini and A. Mantovani, Chem.
Commun., 1977, 132-133.
64. E. Shevchenko, V.,, D. V. Talapin, H. Schnablegger, A. Kornowski, O. Festin, P.
tel-00708600, version 1 - 15 Jun 2012
Svedlindh, M. Haase and H. Weller, J. Am. Chem. Soc., 2005, 125, 9092-9101.
65. E. A. Crespo, M. Ruda and S. Ramos de Debiaggi, Int. J. Hydrogen Energy, 2008, 33,
3561-3565.
66. A. Geissler, M. He, J.-M. Benoit and P. Petit, J. Phys. Chem. C, 2010, 114, 89-92.
Padua and Y. Chauvin, Phys. Chem. Chem. Phys., 2010, 12, 4217-4223.
68. V. Lecocq and H. Olivier-Bourbigou, Oil & Gas Sci. Tech, 2007, 62, 761-773.
69. L. Magna, Y. Chauvin, G. P. Niccolai and J.-M. Basset, Organometallics, 2003, 22,
4418-4425.
70. C. M. Crudden and D. P. Allen, Coord. Chem. Rev., 2004, 248, 2247-2273.
71. U. Hintermair, T. Gutel, A. M. Z. Slawin, D. J. Cole-Hamilton, C. C. Santini and Y.
Chauvin, J. Organometal. Chem., 2008, 693, 2407-2414.
72. D. S. McGuinness, W. Mueller, P. Wasserscheid, K. J. Cavell, B. W. Skelton, A. H.
White and U. Englert, Organometallics, 2002, 21, 175-181.
73. N. D. Clement, K. J. Cavell, C. Jones and C. J. Elsevier, Angew. Chem. Int. Ed., 2004, 43,
1277-1279.
74. D. C. Graham, K. J. Cavell and B. F. Yates, Dalton Trans., 2007, 41, 4650-4658.
75. S. Gruendemann, A. Kovacevic, M. Albrecht, J. W. Faller Robert and H. Crabtree, Chem.
Commun., 2001, 2274-2275.
76. P. Ireland, Thin Solid Films 1997, 304, 1-12.
103
77. S. Murarka and S. Hymes, Crit. Rev. Solid State Mater. Sci. 1995, 20, 87-124.
78. J. Dufourcq, S. Bodnar, G. Gay, D. Lafond, P. Mur, G. Molas, J. Nieto, L. Vandroux, L.
Jodin, F. Gustavo and T. Baron, App. Phys. Lett., 2008, 92.
79. C. C. Santini, J.-M. Basset, T. Gutel, P. Campbell, S. Deleonibus and P.-H. Haumesser,
CEA-LETI /Univ Lyon 1 -CNRS, Fr0901463, 2009.
80. C. C. Santini, J.-M. Basset, T. Gutel, P. Campbell, S. Deleonibus and P.-H. Haumesser,
CEA-LETI /Univ Lyon 1 -CNRS, Fr0901464, 2009.
82. E. Redel, R. Thomann and C. Janiak, Chem. Commun., 2008, 1789-1791.
83. Y. Wang, Z. Cui and Z. Zhang, Mater. Lett., 2004, 58, 3017-3020.
84. A. F. Wells, Structural Inorganic Chemistry, Clarendon Press, Oxford, 1986.
tel-00708600, version 1 - 15 Jun 2012
85. H. Z. D. R. Sadoway, J. Mater. Chem., 2001, 16, 2544.

86. J. Y. Li, Rare Met. Mater. Eng., 1994, 61.
87. S. Nemana, N. L. Okamoto, N. D. Browning and B. C. Gates, Langmuir, 2007, 23, 8845-
8854.
88. S. Z. El Abedin, Trans. Inst. Met. Finish., 2008, 86, 220-226.
89. S. Z. El Abedin and F. Endres, ChemPhysChem, 2006, 7, 58-61.
90. S. Z. El Abedin and F. Endres, Acc. Chem. Res., 2007, 40, 1106-1113.
91. J. Dupont, in Nanoparticles and catalysis, Wiley-VCH, Weinheim, 2008.
93. R. R. Schrock and J. D. Fellmann, J. Am. Chem. Soc., 1978, 100, 3359-3370.
94. F. Favre, H. Olivier-Bourbigou, D. Commereuc and L. Saussine, Chem. Commun., 2001,
1360-1361.
95. P. Pertici, G. Vitulli, M. Paci and L. Porri, Dalton Trans., 1980, 1961-1964.
104
III
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Chapter 3
Imidazolium Ionic Liquids as

Media for Homogeneous
Catalysis
105
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106
Chapter 3 Imidazolium ILs as Media for Homogeneous Catalysis
Chapter 3
Imidazolium Ionic Liquids as Media for Homogeneous
Catalysis
3.1 Introduction .................................................................................................................................. 109
3.2 The influence of the ionic liquid medium on the catalytic hydrogenation of 1,3-cyclohexadiene by
an Osborn-type catalyst............................................................................................................................. 116
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3.2.1 Solvation of 1,3-cyclohexadiene and molecular structure of the mixtures .............................. 117
3.2.1.1 Solubility......................................................................................................................... 117
3.2.1.2 Enthalpy of mixing ......................................................................................................... 118
3.2.1.3 ROESY NMR spectroscopy ........................................................................................... 120
3.2.1.4 Molecular dynamics simulations .................................................................................... 122

1
3.2.1.5 H NMR shift variation with R ....................................................................................... 127
3.2.2 Mass transport in the reaction media ....................................................................................... 129
3.2.3 Hydrogenation of 1,3-cyclohexadiene ..................................................................................... 132
3.2.3.1 Monitoring by UV-vis spectroscopy in both ILs ............................................................ 132
3.2.3.2 CYD catalytic hydrogenation in both ILs ....................................................................... 135
3.2.3.3 Varying the viscosity in [C1C4Im][NTf2]........................................................................ 137
3.3 Conclusion ................................................................................................................................... 140
3.4 Outlooks ....................................................................................................................................... 141
3.5 Experimental Section ................................................................................................................... 142
3.5.1 Materials and methods ............................................................................................................. 142
3.5.2 Synthesis of the catalysts ......................................................................................................... 142
3.5.3 Ligand exchange ...................................................................................................................... 143
107
3.5.4 Reaction with H2...................................................................................................................... 143
3.5.5 Hydrogenation of 1,3-cyclohexadiene ..................................................................................... 143
3.5.6 Solubility and phase diagrams ................................................................................................. 144
3.5.7 Isothermal titration calorimetry ............................................................................................... 145
3.5.8 Density and viscosity ............................................................................................................... 145
3.5.9 NMR spectroscopy .................................................................................................................. 146
3.5.10 Molecular simulation .......................................................................................................... 149
3.6 References .................................................................................................................................... 150

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108
3.1 Introduction
Ionic liquids are up-and-coming solvents for catalysis, with the number of publications in
this field growing at an exponential rate.1-10,11,12 Indeed, the “green” nature of ILs is often cited,
and recyclability is a recurring theme to justify such great interest. This recyclability can be two-
fold, as ILs may act to immobilise certain ionic,13, 14or colloidal catalysts,15 preventing catalyst
leaching; and due to their negligible vapour pressure, they themselves may be recycled more
easily than traditional solvents, the products being recovered by simple distillation or liquid-
liquid extraction.16, 17 For the latter, the extraction solvent is often present during the reaction,
thus many papers describe “biphasic catalysis”.18-22
ILs of course are unlike traditional solvents. As reaction media, they have specific
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properties that may have consequences on the catalytic process. In some catalytic reactions, the
difference between the use of ILs and traditional solvents can be related to the chemical role of
ILs, which may interfere with the reaction. For instance, imidazolium moieties of the IL may be
deprotonated in situ and coordinate to metal centres such as Pd, Ir and Rh as imidazolylidene N-
heterocyclic carbene ligands, as shown in Scheme 1.23, 24 Due to the acidic C2-H, this reaction
can occur under mild conditions and in the absence of a base.25 This has a significant effect on
catalytic reactions. In the case of palladium-catalysed telomerisation of butadiene with methanol,
catalyst deactivation occurs due to the formation of highly stable palladium imidazolylidene
complexes.26 During biphasic Ni-catalysed ethylene oligomerisation in ILs, the formation of
NHCs in situ has also been evidenced by the formation of an imidazolium cation substituted with
an ethyl group on C2, Scheme 2.27
Scheme 1. Typical pathway for in situ NHC formation in imidazolium ILs
109
Scheme 2. Ethyl substituted ionic liquid resulting from the in situ formation of NHC
However, it has also been reported by Hintermair et al. that the nature of such ligands can
have positive effect in on both the thermal stability and selectivity of the resulting catalyst
compared to phosphine ligands.28 Thus the potential for chemical interference may be considered
either an advantage or disadvantage, depending on the desired outcome of the catalytic process.
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It is well worth mentioning that certain ILs themselves exhibit catalytic activity. For
instance Lewis acidic ILs, particularly dialkylimidazolium chloroaluminates, which are amongst
the first described ionic liquids, can be used successfully as both solvent and catalyst
simultaneously. The acidity of such ionic liquids is easily tuned by simply altering the
stoichiometry of the dialkylimidazolium chloride versus the aluminium trichloride; an excess of
the latter leads to the presence of Al2Cl7-. Due both to this and to the fact that aromatics are
highly soluble in IL media, Friedel-Crafts alkylations and acylations occur readily in these dual-
purpose solvents, Scheme 3.6, 29
Scheme 3. Friedel-Crafts acylation catalysed by the choroaluminate anion in ILs
In other cases, differences in reactivity have a purely physical-chemical origin. Numerous

experimental studies have been carried out providing strong evidence for local structuring of
pure ILs, be it through sophisticated NMR spectroscopy focusing on through-space NOE
interactions,30 X-ray diffraction,31, 32,33
or neutron scattering.34 Neutron scattering experiments
have uncovered evidence for significant charge ordering in the IL [C1C2Im][NTf2], even in the
liquid state, while X-ray diffraction patterns of supercooled and liquid imidazolium ionic liquids
110
with varying chain lengths, have found structural heterogeneities that varied in size with the
alkyl chain length, Figure 1.
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Figure 1. X-ray diffraction patterns from the series of supercooled liquid RTILs: [C 1CnIm]Cl, n ) 3, 4, 6, 8, 10, at
25 °C. In the inset the spatial correlation L ) 2π/QMAX, QMAX being the interference peak position, is plotted (circles)
as a function of n, the alkyl chain length,for 4 ≤ n. The corresponding data are also reported for the cases n = 6 and 8
for [C1CnIm][BF4] (squares). 31
Indeed ionic liquids, especially those based on imidazolium, are widely claimed to
exhibit a non-homogenous structure, with close anion-cation association existing throughout the
solution, as demonstrated through molecular simulation,35 and coarse grain modelling.36 The
order and structure therefore depends greatly on both the coordination strength of the anion and
on the alkyl chains which group together in lipophilic domains. Short alkyl chains (n < 4) are too
short to associate with one another, whereas intermediate length chains (4 ≤ n < 10) will form
“pockets”, as seen in Figure 2,35, 37 explaining the heterogeneities observed by X-ray diffraction.
Longer chains lead to mesophases and ionic liquid crystals as demonstrated through SAXS
experiments.38 This therefore leads to the question: how do these self-organised media interact
with different substrates and what is the upshot in catalysis?
111
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Figure 2. Molecular simulations of [C1CnIm][PF6] ionic liquid structures. In a) [C1C2Im][PF6], colouring is used
to distinguish anions from cations, anions being yellow. In b)-f) colouring distinguishes charged species from non-
polar species, red being charged and green being non-polar: b) [C1C2Im][PF6], c) [C1C4Im][PF6], d) [C1C6Im][PF6],
e) [C1C8Im][PF6 and f) [C1C10Im][PF6]
Ionic liquids have been shown to exhibit specific interactions with themselves, so specific
interactions between the ionic liquid and the substrate may also exist and play an important role.
Indeed, molecular simulation and determination of radial distribution functions predict that non-
polar solutes dissolve in non-polar domains, polar solvents dissolve in polar regions, and
amphiphilic solvents, e.g. methanol and acetonitrile display more complicated behaviour.39
Polarity is not the only consideration however, as X-ray structural determination of benzene-
112
[C1C2Im][NTf2] mixtures with various compositions have shown evidence for strong π-cation
interactions, as shown in Figure 3.40 Similarly, through combined ROESY NMR and molecular
simulation studies, such interactions have been shown to exist in toluene-IL mixtures for the
trialkyl IL [C1C1C4Im][NTf2]. By contrast, for the dialkyl IL [C1C4Im][NTf2, π-cation
interactions with toluene are inhibited by the strong H-bond network between anion and cation,
induced by the relatively acidic C2-H. In this case, toluene penetrates the non-polar alkyl regions
of the IL.41 Another NMR study has provided supporting evidence that the nature of the IL, and
thus the interactions within, is crucial in determining the placement of thiiophene in thiophene-IL
mixtures. Figure 4 shows the different hypothesised arrangements for thiophene in the ILs
[C1C1Im][MeOPHO2] and [C1C4Im][SCN] based on this NMR evidence.42. Furthermore, the
arrangement of CS2 dissolved in the IL [C1C5Im][NTf2] has been studied as a function of
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concentration at 295 K by the use of optical heterodyne-detected Raman-induced Kerr effect

spectroscopy. The optical Kerr effect (OKE) spectrum suggest that, at low concentration, CS2
molecules are isolated from each other and mainly localised in the non-polar domains of the IL,
Figure 5.43
Figure 3. Crystal structure of benzene-[C1C2Im][NTf2] inclusion crystal for a 1:1 molar ratio
113
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Figure 4. Proposed structure of thiophene in the ionic liquids [C1C1Im][MeOPHO2] (upper) and [C1C4Im][SCN]
(lower), 42
Figure 5. CS2 molecules are isolated from each other and mainly localised in the nonpolar domains of the IL.43
Finally, issues such as density and viscosity in ionic liquids, which are more significant
than in most traditional solvents, will play an important role in catalysis through dictating the
114
diffusion of molecules in the medium.44, 45, 46 The viscosity varies greatly with the nature of the
IL and, although related to the strength of the cation-anion association, is often difficult to
predict.47-48
In this chapter, we study how in ILs, the activity and selectivity of a model catalytic
reaction (hydrogenation of 1,3-cyclohexadiene, CYD, Scheme 4) are dependent on the solvation
of substrate and of the physical-chemical properties of the resultant catalytic medium.
H2
Cat / IL
Scheme 4. Catalytic hydrogenation of CYD
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115
3.2 The influence of the ionic liquid medium on the catalytic

hydrogenation of 1,3-cyclohexadiene by an Osborn-type catalyst
Selective hydrogenation of 1,3-cyclohexadiene (CYD) into cyclohexene (CYE) can be

carried out, with good conversion rates, using Osborn’s complex [Rh(NBD)(PPh3)2]PF6
(NBD = norbornadiene) in IL media such as [C1C4Im][SbF6] or [C1C4Im][PF6].14 The aim of this
chapter is to study the influence of the nature of the ionic liquid on this catalytic hydrogenation.
As previously mentioned, work carried out in our laboratory has already described the
difference in intermolecular interactions existing in mixtures of toluene in the ILs 1-butyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide, [C1C4Im][NTf2], and 1-butyl-2,3-
dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [C1C1C4Im][NTf2], stronger π-cation
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stacking existing for the latter due to disruption of the anion-cation H-bonding caused by the
methyl group. For a non-aromatic π-system, such as 1,3-cyclohexadiene, solvation is probably a
combination of more subtle interactions with the ionic liquid.
The ILs [C1C4Im][NTf2] and [C1C1C4Im][NTf2] are chosen in order to avoid impurities
such as chloride and water, since they are hydrophobic, liquid at room temperature, and their
purification is well controlled.26 Firstly, the molecular interactions between the ILs and CYD
must be assessed through:
NMR characterisation
study of the microscopic structure of the IL-substrate mixtures
measurement of the thermodynamic properties of mixing (such as the solubility
and the heat of mixing)
determination of the viscosity of the reaction media
measurement of diffusivity of CYD in ILs
Following this, the difference in catalytic performance in the two different media must be
quantified, and explained using the findings from the previously conducted analyses. (Anion
exchange between the IL and the catalyst can be circumvented by replacing Osborn’s complex
with [Rh(COD)(PPh3)2]NTf2, COD = 1,5-cyclooctadiene).
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3.2.1 Solvation of 1,3-cyclohexadiene and molecular structure of the mixtures

3.2.1.1 Solubility
Figure 6 shows cloud-point temperatures as a function of composition for CYD-
[C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2].49,50 The observation of the cloud point with
decreasing the temperature was difficult, especially for the CYD-[C1C1C4Im][NTf2] system,
because in this case the mixtures often remained in a metastable state and cloudiness persisted
despite overheating. Observation of the cloud point with decreasing temperature was not
reproducible during this experiment. Such difficulty with ionic liquid systems has already been
discussed and may be mainly due to the effect of pre-cooling and slow kinetics of demixing.
Consequently, the solubility was determined at only two temperatures.
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Figure 6. Liquid-liquid equilibrium diagrams for the mixture of toluene and [C 1C4Im][NTf2] (o) or
[C1C1C4Im][NTf2 1C4Im][NTf2] ( ) or [C1C1C4Im][NTf2] ( ) xIL = IL molar
fraction: [IL]/([IL]+{CYD]).
The solubility of CYD at 303.15 K, expressed in mole fraction is 0.42 in [C1C4Im][NTf2]

and 0.34 in [C1C1C4Im][NTf2] (see Figure 6) which could indicate less favourable interactions
between CYD and the [C1C1C4Im] ion in comparison with the [C1C4Im] ion. In the temperature
range studied, both systems CYD-[C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2] show behaviour
compatible with the existence of upper critical solution temperatures and very steep liquid-liquid
117
equilibrium lines. In comparison with aromatic molecules in these ILs, CYD is much less
soluble. For instance, the solubility of toluene at 303.15 K expressed in mole fraction is 0.73 in
[C1C4Im][NTf2] and 0.72 in [C1C1C4Im][NTf2],41 the solubility of benzene in [C1C4Im][NTf2]
40
being even higher (mole fraction of 0.78 at 303.15 K). The small difference in solubility of
toluene with respect to benzene can be attributed to the presence of an additional methyl group,
whereas the much lower solubility of CYD is explained by less favourable interactions between
the solute and the ILs. Disruption of the aromatic system changes the interactions between solute
and ionic liquid and thus decreases the solubility.
3.2.1.2 Enthalpy of mixing
The energy involved in the interactions of different solutes dissolved in ILs can be
assessed by measuring the excess molar enthalpy. This was carried out for both systems; CYD-
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[C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2]. The excess molar enthalpy of mixing ΔHmixE was
determined by isothermal titration calorimetry, from the heat effect involved in injections of
small quantities of CYD into the ionic liquid, QCYD. The partial molar excess enthalpy of solute,
HCYDE, was calculated according to equation (1).
E
E H mix QCYD
HCYD (1)
nCYD nCYD
nIL, p,T
where nCYD and nIL denote the quantity of CYD and IL, respectively, ΔHmixE is the excess molar
enthalpy of the entire system (enthalpy of mixing) and ΔnCYD is the quantity of solute per
injection. ΔnCYD was calculated from the injected volumes and the density of CYD was obtained
from the literature. In these calculations, heat due to evaporation of the solute from IL solution is
assumed to be negligible. Hence, no correction for the vapour pressure of the solute was made.
Figure 7 represents partial molar excess enthalpies of CYD in both ILs at 303.15 K as a
function of composition. A larger dispersion of the values (up to 3%), especially at higher
concentration, was observed. At times, before each injection of CYD into the IL, an exothermic
effect was detected, mainly originating from insufficient mixing of both components at the
51
beginning of the injection period. As already observed in the case of aromatic hydrocarbons,
the rate of dissolution of non-polar, low density and low viscosity CYD in the IL is slow and
sometimes leads to formation of a solute-rich layer on the surface of the solution. This is often
118
accompanied by partial evaporation or even polymerisation of CYD before the mixing process
is complete, hence disturbing the measurements. A large number of injections were made to
ensure reliability.
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Figure 7. Partial molar excess enthalpies vs. mole fraction of CYD in the binary mixture with [C 1C4Im][NTf2]( ) or
[C1C1C4Im][NTf2]( ) at 303.15 K. The lines represent functions: HCYDE=1.6285+0.2481xCYD ( ) and
HCYDE=0.8574-0.1518xCYD ( ).xCYD = CYD molar fraction: [CYD]/([IL]+{CYD])
Comparison of [C1C4Im][NTf2] and [C1C1C4Im][NTf2] shows that introduction of an

additional methyl group on C2 carbon of the imidazolium ring strongly affects the interaction
with molecules of CYD, which becomes less favourable. In order to rationalise the differences in
the solvation of CYD in both ILs, and to complement the enthalpic data with structural
information, the microscopic structure of the mixtures was investigated using NMR experiments
and molecular simulation.
The formation of a polymer was observed and confirmed by NMR analysis.52 This side-reaction is attributed to the
fact that CYD has been distilled to eliminate the stabiliser BHT before the physical chemical measurements.
119
Scheme 5. Atom labelling of CYD, 1-butyl-3-methylimidazolium and 1-butyl-2,3-dimethylimidazolium cations.

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3.2.1.3 ROESY NMR spectroscopy

NOESY (nuclear Overhauser effect spectroscopy) experiments exhibited very weak or
null cross peak intensities. Rotating frame NOE experiments (ROESY) allowed us to obtain
positive NOEs irrespective of the long rotational correlation time due to the high viscosity of the
system. In 1H-1H ROESY techniques based on cross-space relaxations, the selective irradiation
of a proton group affects the signal intensities of all proton groups which are spatially close but
not necessarily connected by chemical bonds. The method is based on the assumption of short-
range intermolecular distances (4 – 5 Å).{Frezzato, 2006 #2063} The strength of the ROE signal
is proportional to the inverse sixth power of the distance between the atoms, I 1/r6. In the
liquid state, this relationship is possible if the intermolecular association is tight enough to turn
the intermolecular relaxation into “intramolecular” within the ion pair or ion-molecule
association.53 Highly structured, bulk ionic liquids seem to fulfill these requirements, thus
allowing the use of the intermolecular ROESY to derive lower limits for interionic distances.
Consequently, the intensity of the integrals (ICYD-IL) could be considered as roughly inversely
proportional to the intermolecular distances. The resultant ROESY correlation spectra for CYD-
[C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2], R = 0.5, (R = CYD/IL) are depicted in Figures 8
and 9, respectively.
120
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Figure 8. ROESY NMR spectrum for the mixture of 1,3-cyclohexadiene and [C1C4Im][NTf2] at R = 0.5.
Figure 9. ROESY NMR spectrum for the mixture of 1,3-cyclohexadiene and [C1C1C4Im][NTf2] at R = 0.5.
121
Molecular mechanics calculations have been performed, using the SYBYL software with
the TRIPOS force field,54on isolated pairs of CYD and imidazolium cations. Intermolecular
distances were fixed using results from NMR ROESY experiments and the energy of both
systems, CYD-[C1C4Im] and CYD-[C1C1C4Im], were minimised. The average distances between
molecules of CYD and the imidazolium cations were determined from their geometry and
orientation at the potential energy minimum. This model, pictured in Figure 10, suggests that
CYD is probably located nearer to the butyl chain of [C1C4Im][NTf2], the π-bonds being oriented
towards the imidazolium cation, a configuration similar to that previously observed for toluene.41
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Figure 10. Representation of molecular positions in saturated solutions of CYD-[C1C4Im][NTf2] (upper) and CYD-
[C1C1C4Im][NTf2] (lower) from ROESY NMR extrapolation.
3.2.1.4 Molecular dynamics simulations

Access to the microscopic structure of the mixtures in the condensed liquid phase is
possible using molecular dynamics simulation with all atoms explicitly present and periodic
boundary conditions employed to represent a virtually infinite system. Condensed-phase
simulations take into account all the two-body interactions from the environment of each
122
molecule or ion. The molecular simulation details are given in the experimental section 3.5.10. In
Figure 11 are plotted the site-site radial distribution functions — the probability of finding pairs
of atoms at a given distance, compared to the average — between the hydrogens on Cβ of CYD,
Hβ, and selected atoms of the [C1C4Im] and [C1C1C4Im] cations at R = 0.5 (atoms are labelled as
indicated in Scheme 5). In both cases, there is a higher probability (a stronger association) of
finding all hydrogen atoms of CYD near the side chain than in the vicinity of the aromatic
nucleus region of imidazolium cation. This means that CYD is preferentially solvated in the non-
polar domain of the ILs, as already observed for saturated hydrocarbons and for the methyl group
of toluene. This orientation effect relative to the cation is less distinct for CYD than for toluene,
41
as expected given the weaker -cation interactions.
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Figure 11. Radial distribution functions between hydrogen on Cβ of CYD, Hβ, and selected sites in the [C 1C4Im]
cation (top) and [C1C1C4Im] cation (bottom), for R = 0.5. Atoms are labeled as indicated in Scheme 5.
Figure 12 represents the comparison of the radial distribution functions of the mixtures
CYD-[C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2], again at R = 0.5, between hydrogen on Cβ
123
and Cα of CYD and C2 of the imidazolium rings. It can be seen that both these hydrogen atoms
are found with a higher probability closer to C2 in [C1C1C4Im][NTf2] than in [C1C4Im][NTf2].
The strong hydrogen bond between C2-H and the anion in [C1C4Im][NTf2] prevents such an
interaction with CYD. This observation is consistent with the distances between the IL cations
and CYD obtained from ROESY experiments and molecular mechanics calculations on isolated
pairs, as seen in Figure 10.
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Figure 12. Comparison of site-site radial distribution functions between chosen atoms in CYD and the cations, in
CYD-[C1C4Im][NTf2] (top) and CYD-[C1C1C4Im][NTf2] (bottom) for R = 0.5. Atoms are labeled as indicated in
Scheme 5.
Detailed structural features are much better perceived in 3-dimensional spatial

distribution functions. In Figure 13 is represented the distribution of ions around a CYD
molecule. In blue is plotted the iso-surface corresponding to a local density of twice the average
density of C2 carbon atoms of the imidazolium cations. Cation headgroups (the blue regions) are
located above and below the CYD ring, interacting preferentially with the π-system of CYD. It
can be seen that the terminal carbons of the alkyl side chain, C9, (the grey regions) surround
124
CYD molecule. Oxygen atoms of the NTf2- anion (plotted in red) are found in the plane of CYD
interacting with the hydrogen atoms of the double bonds. Similar results have been previously
obtained for toluene in the same ILs. 41 This shows that although in CYD the π-system is smaller
than that of a fully aromatic system, it still determines the structure of the solvation shell in ILs
with cations positioned above and below the plane of CYD and anion in the plane.
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Figure 13. Spatial distribution functions around the C2 carbon of CYD in CYD-[C1C4Im][NTf2] (left) and CYD-
[C1C1C4Im][NTf2] (right) at R = 0.5. In blue is plotted the iso-surface corresponding to a local density of twice the
average density of C2 carbon of the imidazolium cations. In grey is plotted the iso-surface corresponding to a local
density of twice the average density of terminal methyl carbons from the butyl side chain, C9. In red is plotted the
iso-surface corresponding to a local density of twice the average density of oxygen atoms from the NTf 2- anion.
Oxygen atoms are located in the CYD plane interacting with hydrogen atoms of double bonds, Hα and Hβ.
Figure 14 shows spatial distribution functions around the [C1C4Im] and the [C1C1C4Im]
cations. With both cations, CYD (the white regions) is preferentially located above and below
the plane of the imidazolium ring at distances greater than those of the closest cation-anion pairs.
125
In red is plotted the iso-surface corresponding to a local density of 4 times the average density of
the oxygen atoms from [NTf2] anions. As can be seen, for [C1C4Im][NTf2] the probability of
finding the oxygen of [NTf2] near the C2-H of the imidazolium cation is higher than the carbon
of CYD, indicating a strong H-bond. The situation is completely different for [C1C1C4Im][NTf2],
where the probability of finding the carbon of CYD near the C2 of the cation is higher than that
of the oxygen atoms of [NTf2]. As already found in case of solvation of toluene,41interactions of
the [C1C1C4Im] cation with the anion are mainly through H4, H5 and also through the nitrogen
atoms, N1 and N3, whereas in [C1C4Im] cation-anion interactions are mainly through C2-H bonds.
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Figure 14. Spatial distribution functions around the C2 carbon of the cations in CYD-[C1C4Im][NTf2] (left) and
CYD-[C1C1C4Im][NTf2] (right) at R = 0.5. Above and below are different views of the same iso-surfaces. In white is
plotted the iso-surface corresponding to a local density of twice the average density of Cα of CYD. In red is plotted
the iso-surface corresponding to a local density of 4 times the average density of oxygen atoms from the NTf 2–
anion.
126
3.2.1.5 1H NMR shift variation with R

We have also examined the effect of introducing CYD into each IL on the chemical shifts
of all hydrogen atoms of the IL, Tables 1 and 2. Curves of mean chemical shift change, Δδ, are
plotted with respect to R in Figure 15. Atom labelling is depicted in Scheme 5.
Table 1. The 1H NMR chemical shifts of neat [C1C4Im][NTf2], and those of the IL, in the presence of CYD.
R = [CYD]/[IL]. Protons numbered as indicated in Scheme 5.
Proton. R0=0 R1=0.11 Δ(R1- R0) R2=0.21 Δ(R2- R0) R3=0.34 Δ(R3- R0) R4=0.54 Δ(R4- R0) R5=0.81 Δ(R5- R0)
2 8.60 8.62 0.02 8.64 0.04 8.67 0.07 8.71 0.11 8.76 0.16
4 7.45 7.52 0.07 7.54 0.09 7.56 0.11 7.59 0.14 7.63 0.18
5 7.38 7.44 0.06 7.46 0.08 7.49 0.11 7.52 0.14 7.55 0.17
6 4.14 4.22 0.08 4.24 0.10 4.27 0.13 4.30 0.16 4.34 0.20
1 3.91 3.95 0.04 3.97 0.06 3.99 0.08 4.02 0.11 4.07 0.16
7 1.86 1.91 0.05 1.93 0.07 1.95 0.09 1.98 0.12 2.03 0.17
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8 1.36 1.39 0.03 1.42 0.06 1.44 0.08 1.48 0.12 1.53 0.17
9 0.95 0.95 0.00 0.98 0.03 1.01 0.06 1.05 0.10 1.10 0.15
mean Δ 0.04 0.07 0.09 0.13 0.17
Table 2. The 1H NMR chemical shifts of neat [C1C1C4Im][NTf2], and those of the IL, in the presence of CYD.
R = [CYD]/[IL]. Protons numbered as indicated in Scheme 5.
Proton. R0=0 R1=0.08 Δ(R1- R0) R2=0.18 Δ(R2- R0) R3=0.30 Δ(R3- R0) R4=0.40 Δ(R4- R0) R5=0.69 Δ(R5- R0)
4 7.35 7.36 0.01 7.39 0.04 7.41 0.06 7.42 0.07 7.46 0.11
5 7.28 7.29 0.01 7.32 0.04 7.34 0.06 7.36 0.08 7.40 0.12
6 4.08 4.09 0.01 4.12 0.04 4.14 0.06 4.16 0.08 4.20 0.12
1 3.76 3.78 0.02 3.81 0.05 3.83 0.07 3.85 0.09 3.89 0.13
2 2.57 2.59 0.02 2.62 0.05 2.64 0.07 2.66 0.09 2.71 0.14
7 1.77 1.79 0.02 1.82 0.05 1.85 0.08 1.87 0.10 1.91 0.14
8 1.36 1.37 0.01 1.41 0.05 1.44 0.08 1.46 0.10 1.51 0.15
9 0.91 0.93 0.02 0.97 0.06 1.00 0.09 1.02 0.11 1.08 0.17
mean Δ 0.02 0.05 0.07 0.09 0.14
Unlike in the case of toluene-IL mixtures,41 it is found that all peaks are generally shifted
downfield with increasing molar ratio of CYD, R = [CYD]/[IL], demonstrating the deshielding
effect CYD has on all hydrogen nuclei. The upfield shift of IL proton NMR shifts in toluene-IL
mixtures was attributed to π-cation interactions, which according to our molecular models do not
exist in the case of CYD.
Excluding the first point of each series, Δδ versus R follows a straight line, Figure 15.
The slopes (0.17 ppm for [C1C4Im][NTf2]; 0.18 ppm for [C1C1C4Im][NTf2]) are almost identical
for both ILs. The similar linear variation of the deshielding effect for both ILs shows that no
127
structural reorganisation occurs with increasing CYD concentration. Indeed, a lipophilic

substrate that displays little specific interactions with the IL moieties, such as CYD, will be
mostly solvated in the non-polar pockets, causing them to swell. When these pockets become
saturated, demixing will occur. Furthermore, the absolute mean chemical shift change, |Δδ|, is
greater in the IL [C1C4Im][NTf2] i.e. CYD has a stronger impact on the electronic structure of
this IL.
The first point of each series lies beneath the linear regression. This signifies that with the
incorporation of very small quantities of CYD, i.e. R < 0.2, a reorganisation of the medium with
respect to the pure IL occurs. This is more significant in the case of [C1C4Im][NTf2], yet again
suggesting stronger specific interactions in this case.
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0.2
0.18
0.16
0.14
Mean Δδ / ppm
0.12
0.1
0.08 [C1C4Im][NTf2]
0.06 [C1C1C4Im][NTf2]
0.04
0.02
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
R
Figure 15. Mean deviation of proton chemical shifts in IL-CYD mixtures with respect to R
The variation of the CYD chemical shifts when changing R were also studied and are
tabulated in Table 3. As for the shifts of the IL moieties, CYD shifts are shifted downfield
demonstrating once again the deshielding effect of CYD, even on itself. At low concentration the
CYD molecules interact mostly with the alkyl chains of the ILs, but as the concentration
increases, CYD molecules will also interact with one another.
128
Table 3. 1H NMR chemical shifts of CYD in the ILs. R = [CYD]/[IL]. Protons labelled as indicated in Scheme 5.
[C1C4Im][NTf2]/CYD [C1C1C4Im][NTf2]/CYD
R R
α β γ α β γ
0.11 5.84 5.79 2.08 0.08 5.81 5.75 2.06
0.21 5.88 5.81 2.11 0.18 5.85 5.78 2.10
0.34 5.92 5.85 2.15 0.30 5.87 5.82 2.13
0.54 5.94 5.88 2.19 0.40 5.91 5.83 2.16
0.81 6.00 5.93 2.41 0.69 5.97 5.90 2.22
3.2.2 Mass transport in the reaction media

Differences in the rate of catalytic hydrogenation of CYD could also be related to
differences in thermophysical properties of the reaction media, which affect the mobility of
molecules.
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Density and Viscosity

The density and viscosity of the mixtures of CYD-[C1C4Im][NTf2] and CYD-
[C1C1C4Im][NTf2] were measured at 298.15 K and atmospheric pressure, at various molar ratios
R (Table 4). The additional methyl group on the imidazolium carbon C2 in [C1C1C4Im][NTf2]
naturally lowers both the mass and molar density of the liquid in comparison with
[C1C4Im][NTf2]. Furthermore, the viscosity of pure [C1C1C4Im][NTf2] and also of its mixture
with CYD is roughly twice that of [C1C4Im][NTf2], as reported in Table 4. For both ionic liquids
the viscosity of the mixtures is seen to drop sharply with increasing CYD concentration.
Table 4. Density and viscosity, at 298.15 K and atmospheric pressure, of mixtures of CYD-[C1C4Im][NTf2] and
CYD-[C1C1C4Im][NTf2] at R = CYD/IL.
R xCYD ρ (g/mL) η (mPas) R xCYD ρ (g/mL) η (mPas)
[C1C4Im][NTf2] [C1C1C4Im][NTf2]
0.000 0.000 1.4376 48.5 0.000 0.000 1.4177 105
0.100 0.091 1.4202 44.0 0.101 0.091 1.4013 83.0
0.156 0.135 1.4081 40.0 0.201 0.167 1.3858 67.2
0.200 0.167 1.3999 37.0 0.250 0.200 1.3784 60.9
0.248 0.199 1.3937 35.4 0.304 0.233 1.3705 54.5
0.300 0.231 1.3874 33.3 0.407 0.289 1.3538 49.8
0.397 0.284 1.3718 31.0 0.510 0.338 1.3442 47.1
0.498 0.333 1.3597 24.8
129
Diffusivity
Another possible way to obtain information on how the media influences the mobility of
molecules is to determine their diffusion coefficients, D, by NMR spectroscopy. Diffusion Order
SpectroscopY, DOSY*, is an NMR diffusion experiment, which provides a way to separate the
different compounds in a mixture, based on the differing translational diffusion coefficients (and
therefore differences in the size and shape of the molecule, as well as physical properties of the
surrounding environment such as viscosity, temperature, etc.) of each chemical species in
solution.
Generally, according to the Stokes-Einstein equation (2), the diffusion coefficient is
inversely proportional to the viscosity of the medium.
k BT
D (2)
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6 rH
kB = Boltzman constant, rH = hydrodynamic radius
For instance, when R is around 0.5, the diffusion coefficients found for CYD are
187.5 µm2/s in [C1C4Im][NTf2] against 97 µm2/s in [C1C1C4Im][NTf2], i.e. diffusion of CYD in
[C1C4Im][NTf2] is 1.9 times faster than in [C1C1C4Im][NTf2] in agreement with their viscosity
ratio.
The diffusion coefficients (D) of CYD in both ILs while increasing R were thus
determined from extrapolation of DOSY NMR data, and are plotted in Figure 16. The diffusion
coefficients were found to increase with R in both ILs.
*
see experimental section 3.5.9 for further details
130
3.00E-10
[C1C4Im][NTf2]
2.50E-10
[C1C1C4Im][NTf2]
2.00E-10
D / µm2 /s
1.50E-10
1.00E-10
5.00E-11
0.00E+00
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0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

R
Figure 16. D for CYD in CYD-IL mixtures plotted as a function of R
When η-1 is plotted as a function of D an interesting phenomenon is observed as seen in

Figure 17. Here, the relationship is not perfectly linear as predicted by the Stokes-Einstein
equation (2), yet seems to incorporate two components with different gradients.
3 1.8
[C1C4Im][NTf2] 1.6
2.5 [C1C1C4Im][NTf2]
grad 2 = 3.8 10 -9 1.4
grad 2 = 3.4 10 -9
D / 10 -10 µm2 s-1
D / 10 -10 µm2 s-1
2 1.2
1
1.5
0.8
grad 1 = 5.6 10 -9 grad 1 = 5.6 10 -9
1 0.6
0.4 grad 1: grad 2 = 1.6
0.5 grad 1: grad 2 = 1.5
0.2
0 0
0 0.02 0.04 0.06 0.08 0 0.01 0.02 0.03 0.04
η-1 / (mPa.s)-1 η-1 / (mPa.s)-1
Figure 17. Calculated inverse viscosity η-1 plotted as a function of D for CYD in CYD-IL mixtures.
This may indicate different mobility mechanism for low and high concentration mixtures
i.e. for different viscosity. Indeed, in certain cases the Stokes-Einstein model may not be
131
applicable. The predecessor of the Stokes-Einstein equation, described by Sutherland,55 takes

into account a sliding friction coefficient of molecules, β (3), based on the intermolecular
interactions. For the perfectly “sticking surface” (strong intermolecular interactions), β → ∞, and
the Sutherland coefficient, θ, tends to 6, i.e. equation (3) is reduced to the Stokes-Einstein
equation (2). On the other hand, for a perfectly “sliding surface”, i.e. one that exhibits no
interactions with the surrounding medium, β → 0, therefore θ → 4, as in equation (4).
k BT 1 2 / rH
D 6 (3)
rH 1 3 / rH
k BT
D (4)
4 rH
Indeed, a recent study of the diffusion of ferrocene in imidazolium ionic liquids found
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that due to the lack of specific interactions between ferrocene and the surrounding medium, the
Sutherland coefficient of 4 was more applicable.46 We have already demonstrated in section
3.2.1 that CYD does not display strong specific interactions with the IL. This brings into
question the suitability of the Stokes-Einstein equation in the case under study.
When we calculate the ratio of the gradients of the curves of η-1 plotted as a function of
D, Figure 17, at low vs. high concentration of CYD, we find a ratio of 1.5 for [C1C4Im][NTf2]
and 1.6 for [C1C1C4Im][NTf2]. This could be explained by Stokes-Einstein behaviour at high
concentration (i.e. low viscosity) θ = 6, and “sliding surface” behaviour at low concentration,
θ = 4. This corroborates the lack of intermolecular interactions found between the CYD and the
ILs. More measurements are underway to confirm this.
Nevertheless, it is clear that the viscosity is a complex issue that must be taken into
account when ILs are used as media for catalysis.
3.2.3 Hydrogenation of 1,3-cyclohexadiene
In organic solvents, during the hydrogenation of 1,3-cyclohexadiene, the catalyst first
undergoes a ligand exchange yielding [Rh(CYD)(PPh3)2]+. This occurs more rapidly than the rate
at which it then reacts with H2.56, 57
The two reaction steps, depicted in Scheme 6, were
investigated in both ILs.
3.2.3.1 Monitoring by UV-vis spectroscopy in both ILs
Firstly, [Rh(CYD)(PPh3)2]NTf2 was synthesised from [Rh(COD)(PPh3)2]NTf2 and fully
characterised. As [Rh(COD)(PPh3)2]NTf2 is yellow ( max = 450 nm) and [Rh(CYD)(PPh3)2]NTf2
132
is red ( max = 500 nm), the ligand exchange COD-CYD could be monitored by UV-Vis
spectroscopy ( = 500 nm) in both ILs, as shown in Figure 18. This reaction is much slower in
[C1C1C4Im][NTf2] than in [C1C4Im][NTf2].
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Scheme 6. Ligand exchange and catalytic cycle for the hydrogenation of CYD using an Osborn-type catalyst in ILs
133
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Figure 18. Evolution as a function of time of the ligand exchange reaction COD-CYD for
[Rh(COD)(PPh3)2]NTf2 in [C1C4Im][NTf2] (full line) and [C1C1C4Im][NTf2] (dashed line) monitored at = 500 nm
by UV-Vis spectroscopy. UV-visible spectra of [Rh(COD)(PPh3)2]NTf2 and [Rh(CYD)(PPh3)2]NTf2 are provided in
section 3.5.3
Following this, the red solutions of [Rh(CYD)(PPh3)2]NTf2 in [C1C4Im][NTf2] or

[C1C1C4Im][NTf2] were exposed to hydrogen, leading to discolouration with the concomitant
formation of CYE. This hydrogenation reaction of CYD in [Rh(CYD)(PPh3)2]NTf2 was also
monitored by UV-Vis spectroscopy in both ILs, the absorbances represented in Figure 19. The
results indicate that the hydrogenation step is also faster in [C1C4Im][NTf2] than in
[C1C1C4Im][NTf2]. The two processes, however, do not occur on the same time scale (hours
versus seconds) and, as in organic solvents, ligand exchange is faster than hydrogenation. We
can conclude therefore, in accordance with the literature,56, 57 that in the hydrogenation of CYD,
this attack by H2 is the rate-determining step (Scheme 7).
134
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Figure 19. Evolution of the absorbance at = 500 nm as a function of time during the hydrogenation reaction of
CYD in the presence of [Rh(CYD)(PPh3)2]NTf2 in [C1C4Im][NTf2]( ) and [C1C1C4Im][NTf2]( ).
Scheme 7. The two steps involved in the catalytic hydrogenation of CYD, the attack by H 2 being rate-
determining.
3.2.3.2 CYD catalytic hydrogenation in both ILs

In the hydrogenation experiment the appropriate quantity of CYD was added to the
yellow solution of [Rh(COD)(PPh3)2]NTf2 in [C1C4Im][NTf2] or [C1C1C4Im][NTf2] to reach a
molar ratio between CYD and IL R = 0.5, corresponding to a molar ratio substrate/Rh atom
r = 500. The resulting red solution was stirred under 1.2 bar of hydrogen at 303 K. The formation
of cyclohexene (CYE) was followed by GC analysis. Note that CYE is less soluble than CYD in
both IL media so the system will tend to become biphasic during the course of the reaction. In
order to avoid errors in the determination of the composition of the reaction mixture, resulting
from the heterogeneity of the system, the conversion was measured using GC analysis of the
135
entire reaction system after dissolution in a mixture of acetonitrile and toluene 99:1. Each point,
repeated at least twice, presented in Figure 20, corresponds to a different experiment
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Figure 20. Hydrogenation of CYD at 303 K under 1.2 bar H2 (R = 0.5 and r = n(CYD)/n(Rh) = 500) in
[C1C4Im][NTf2]( ) and [C1C1C4Im][NTf2]( ).
As can be seen in Figure 18, hydrogenation of CYD in both ILs by

[Rh(COD)(PPh3)2]NTf2 leads quantitatively and selectively to CYE. In both cases, no significant
amount (less than 2 % at high or complete conversion) of cyclohexane (CYA) was detected by
GC. As described in the literature, the rate of CYD reduction remains constant until near 100%
conversion (1 mol of H2 absorbed per CYD) and CYE is produced quantitatively before it is
hydrogenated to CYA.56, 57 In [C1C4Im][NTf2] the conversion is complete in 2 h. This result is
56, 57
similar to that observed in organic solvents, and in other ionic liquids, such as
[C1C4Im][PF6] or [C1C4Im][SbF6].14 In [C1C1C4Im][NTf2], only 50 % conversion is reached after
2 h with an initial rate of hydrogenation ca. half of that in [C1C4Im][NTf2].
When all possible experimental factors are identical ([CYD], [Rh], pressure, temperature,
stirring), the fact that both reaction steps proceed twice as fast in a medium that is half as viscous
([C1C4Im][NTf2]) would indicate that the difference in reactivity can be mainly assigned to the
difference in viscosity, and therefore in mass transport, of CYD in the exchange reaction and
both H2 and CYD in the hydrogenation reaction.
136
3.2.3.3 Varying the viscosity in [C1C4Im][NTf2]

To confirm the dependence of the rate of reaction on the mass transport, the viscosity of
the medium may be varied, by changing the CYD concentration in [C1C4Im][NTf2] as previously
demonstrated in section 3.2.2. Therefore for [C1C4Im][NTf2], solutions of CYD were prepared as
described in Table 3.
Table 3. Chosen compositions for catalytic media

R 0.5 0.4 0.3 0.2 0.1
CYD (g) 0.2268 0.1865 0.1438 0.0987 0.0508
LI (g) 2.4531 2.5211 2.5930 2.6690 2.7497
Rh complex (g) 0.0029 0.0024 0.0018 0.0013 0.0006
CYD (mmol) 2.8301 2.3269 1.7949 1.2317 0.6345
LI (mmol) 5.6603 5.8171 5.9830 6.1585 6.3446
Rh complex (mmol) 0.0028 0.0023 0.0018 0.0012 0.0006
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In these conditions, at 303 K, and under 1.2 bar H2, conversion curves for different values
of R are plotted in Figure 21. It can clearly be seen that the rate of this reaction increases with
increasing molar ratio R. When R = 0.1, the conversion rate is found to be very low, values
obtained falling within the experimental error, thus this result is not depicted in Figure 21.
45
40
R = 0.5
35
R = 0.4
30
R = 0.3
Conversion %
25 R = 0.2
20
15
10
0
0 10 20 30 40 50 60 70
Time / mins
Figure 21. Conversion curves for the hydrogenation of CYD with varying molar ratio R = CYD/IL, in
[C1C4Im][NTf2]
137
From literature data and previous results obtained by UV, we hypothesised that the rate
determining step in this reaction is the attack by H2 on the catalyst and not the coordination of
the substrate. In such situations the rate law should be expressed as (5). 58
rate = k [MS][H2] (5)
As the coordination of the substrate to the catalyst is rapid, we can consider the
concentration of substrate-coordinated catalyst, [MS] in (5), equal to the concentration of
catalyst.
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The concentration and diffusivity of H2 in these media (IL:CYD mixture) has been
neither measured nor calculated. Even in neat ILs, no experimental data were found on the
diffusivity of hydrogen. Nevertheless, the diffusivity is expected to be inversely proportional to
the viscosity of the liquid medium since H2 interacts weakly with ILs59-62
In an attempt to establish a rough approximation to the rate law of this reaction, a graph is
plotted of the initial reaction rate versus a combination of these known and controlled variables,
potentially affecting the rate of reaction, i.e. concentration of CYD and catalyst, also including a
-1
term for the viscosity, . As seen in Figure 22, this gives us a near linear relationship, passing
close to origin, indicating that the rate varies inversely with viscosity as expected from previous
results. The rate also varies linearly with the concentration of both catalyst and substrate. (Note
that plots accounting for only one or two of these variables do not give straight lines.) Our curve
-1
therefore seems to indicate that the rate is proportional to [Rh][CYD] .
138
160
140
initial rate /(10-6 mol L-1 s-1 )
120
100
80
60
40
20
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
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[Rh].[CYD].η-1 / mol 2 L-2 Pa -1 s-1
Figure 22. linear relationship of initial rate against the inverse viscosity measured experimentally
It is clear that the system under investigation is complex. To establish the correct rate law
for this reaction, the solubility of H2 in ILs, CYD and IL-CYD binary mixtures must be
accurately measured. We must also determine the effect of changing pressure on both the
solubility of H2 in the media and the viscosity. Furthermore, conductivity must be taken into
account as this may affect the mobility of the ionic catalyst.63
139
3.3 Conclusion
In this chapter, we have attempted to determine the physical-chemical parameters

influencing the catalytic activity of an Osborn-type catalyst [Rh(COD)(PPh3)2]NTf2 in the
hydrogenation of 1,3-cyclohexadiene CYD performed in the ionic liquids 1-butyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide, [C1C4Im][NTf2] and 1-butyl-2,3-
dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [C1C1C4Im][NTf2].
Firstly, the solvation of CYD in the two ILs was investigated by molecular dynamics
simulations, ROESY NMR experiments and compared to previous results involving toluene. In
both ILs, CYD is found to be located in the lipophilic domains. In [C1C1C4][NTf2], CYD is
found closer to the C2-Me, whereas in [C1C4Im][NTf2], strong interactions between C2-H and the
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anion [NTf2] do not allow for such proximity.

Unlike for toluene, it was found that that no strong interactions (e.g. π-cation) exist
between CYD and either of the cations, while calorimetric measurements showed that the
existing weak interactions are more favourable in the case of [C1C4Im][NTf2]. These results
show that solvation phenomena of the substrate should have little impact on the catalytic activity.
Secondly the role of mass transport factors has been studied in both ILs. For this, the
viscosity, η, of CYD-IL mixtures of various molar ratios, R = CYD/IL, was measured, and
shown to vary radically with changing R. The viscosity values measured in [C1C1C4Im][NTf2]
were consistently found to be roughly double those measured in [C1C4Im][NTf2].
The diffusion D of CYD in both ILs while varying R was also experimentally determined
by DOSY NMR. We observed that in these media, D does not vary perfectly linearly with η-1, as
predicted by the Stokes-Einstein equation, suggesting different diffusion behaviour at low and
high R. At high R, i.e. low viscosity, the Stokes-Einstein relationship holds, whereas at low R,
i.e. high viscosity, fluid “sliding surface” behaviour seems more suitable indicating little sliding
friction between the molecules. For the latter case, the Sutherland factor of 6 in the Stokes-
Einstein equation is replaced by 4.
k BT k BT
D à D
6 rH 4 rH
The chosen model catalytic reaction was the hydrogenation of 1,3-cyclohexadiene (CYD)
with which occurs in two steps: the ligand exchange [Rh(COD)(PPh3)2]NTf2 to
140
[Rh(CYD)(PPh3)2]NTf2, and the catalytic hydrogenation of CYD itself (COD=1,5-

cyclooctadiene). It was found that both steps, monitored here by UV-vis spectroscopy, are twice
as fast in [C1C4Im][NTf2], implying that the reaction rate is strongly dependent on the viscosity
and diffusion of the substrate.
Furthermore, when the reaction is performed in [C1C4Im][NTf2] whilst varying R, the

initial rate is found to be inversely proportional to η confirming that for this hydrogenation
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reaction the viscosity and thus mass transport is indeed the deciding factor when performed in
ILs.
The exact kinetic rate law cannot be determined without precise knowledge of H2
solubility and diffusivity in the media and also studies of conductivity and its potential effect on
the mobility of the ionic catalyst. This work is currently underway.
We have successfully demonstrated in this chapter that to fully understand the kinetics of
catalytic processes carried out in IL media, a comprehensive study of all physical-chemical
variables is necessary. Consequently, when comparing literature data on catalytic activity in ILs
the differences in physical-chemical properties must be taken into account, and may shed light
on differences noted. In the case under study it has been found that mass transport factors play a
decisive role.
3.4 Outlooks
For the hydrogenation of CYD in these ILs, we have demonstrated that the rate
determining step involves the insertion of H2. Future work is planned to determine the rate law of
this reaction through a full kinetic study varying conditions such as H2 pressure. For this, due to
the complicated viscosity-dependent behaviour and the interesting solvation properties of ILs, a
study of the viscosity and H2 solubility dependence on H2 pressure must first be undertaken.
Also, a study of conductivity in CYD-IL mixtures, with varying R may give useful information
on the mobility of the ionic catalyst in the different media.
141
Finally, as aromatic substrates such as toluene have already been shown to display more
complicated behaviour when dissolved in ILs, i.e. π-cation interactions, it may be interesting to
observe the effect of such interactions in catalysis.
3.5 Experimental Section
3.5.1 Materials and methods

1-methylimidazole (>99%, Aldrich) and 1,2-dimethylimidazole (>98%, Aldrich) were
distilled prior to use. Anhydrous 1,3-cyclohexadiene (99.8%, Aldrich) and 1,3-cyclohexadiene
stabilised (96%, Acros Organics, stabilised with 50 ppm of 2,6-di-tert-butyl-4-methylphenol,
BHT) distilled over NaK alloy and stored on zeolites were used for the reaction and the physical
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chemical measurements, respectively. Bis(trifluoromethanesulphonyl)imide lithium salt (>99%,

Solvionic) and [Rh(COD)Cl]2 (>99%, Strem) were used without further purification. All other
reagents and solvents were commercially available and were used as received. Ionic liquids,
synthesised as previously reported,26 were dried overnight under high vacuum and stored in a
glovebox (Jacomex) in order to guarantee rigorously anhydrous products.
3.5.2 Synthesis of the catalysts
56
[Rh(COD)(PPh3)2]NTf2: The procedure followed was adapted from the literature. A
mixture of [Rh(COD)Cl]2 (100 mg, 0.2 mmol) dissolved in 2 mL of dichloromethane and of
LiNTf2 (107 mg, 0.37 mmol) dissolved in 2 mL of water was stirred vigorously while
triphenylphosphine (405 mg, 1.5 mmol) was added. After 2 h, the dichloromethane layer was
removed, washed three times with 2 mL of water and dried over anhydrous Na2SO4. Ethanol (1
mL) and diethyl ether (2 mL) were slowly added to complete crystallisation. The orange crystals
were filtered off and dried under reduced pressure. Yield: 200 mg (99%). 1H NMR (300 MHz,
CD2Cl2): = 2.2 (m, 8H), 4.6 (s, 4H), 7.5 (m, 30H). 31P NMR (121 MHz, CD2Cl2): = 23.6 with
103
JRh-P = 147 Hz. Rh NMR (500 MHz, CD2Cl2): = -80 ppm with JRh—P = 147 Hz. Mass
spectrometry (ESI): positive mode: m/z= 473 Rh(COD)(PPh3)+; 627 Rh(PPh3)2+. UV-Vis
spectroscopy (6.6 mg of [Rh(COD)(PPh3)2]NTf2 dissolved in 2 mL of one of ionic liquids,
[C1C4Im][NTf2] or [C1C1C4Im][NTf2]); spectrum recorded at max = 450 nm.
[Rh(CYD)(PPh3)2]NTf2 : [Rh(COD)(PPh3)2]NTf2 (100 mg, 9.84×10-5 mol) was dissolved
in 1 mL of CYD. After 10 min, the excess of solvent was removed under reduced pressure.
142
Yield: 100 mg (99%). 1H NMR (300 MHz, CD2Cl2): = 2.1 (s, 2H), 5.3 (s, 2H), 7.5 (m, 30H).
31
P NMR (121 MHz, CD2Cl2): = 25.2ppm with JRh-P = 17 Hz. Mass spectrometry (ESI):
positive mode: m/z=707 Rh(cyclohexadiène)(PPh3)2+; m/z=627 Rh(PPh3)2+. UV-Vis
spectroscopy (6.6 mg of [Rh(CYD)(PPh3)2]NTf2 dissolved in 2 mL of one of ionic liquids,
[C1C4Im][NTf2] or [C1C1C4Im][NTf2]); spectrum recorded at max = 500 nm.
3.5.3 Ligand exchange
Ligand exchange in [Rh(CYD)(PPh3)2]NTf2 was followed by UV-Vis spectroscopy.
CYD (0.15 mL, 1.6 mmol) was added to a system of [Rh(COD)(PPh3)2]NTf2 (1.6 mg, 1.6 µmol)
in one of the ionic liquids, [C1C4Im][NTf2] or [C1C1C4Im][NTf2] (1 mL). The UV-visible spectra
of 1 mL of the solution were recorded on the Perkin-Elmer LAMBDA 950 Spectrophotometer in
stirred and closed UV cells at max = 500 nm every second. The spectra for both complexes are
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depicted in Figure 23.

4.0 4.0
3.5 3.5
3.0 3.0
2.5 2.5
Absorbance
Absorbance
2.0 2.0
1.5 1.5
1.0 1.0
0.5 0.5
0.0 0.0
400 450 500 550 600 650 700 750 800 400 450 500 550 600 650 700 750 800
λ (nm) λ (nm)
Figure 23. UV-vis absorption spectra for [Rh(COD)PPh3] (left), and [Rh(CYD)PPh3] (right)
3.5.4 Reaction with H2
[Rh(CYD)(PPh3)2]NTf2 (8 mg, 8.1×10-6 mmol) was dissolved in one of the ionic liquids,
[C1C4Im][NTf2] or [C1C1C4Im][NTf2] (5 mL) and pressurised under 1.2 bar of hydrogen. The
UV-visible spectra of 1 mL of the solution were recorded at a given time at max = 500 nm.
3.5.5 Hydrogenation of 1,3-cyclohexadiene
The hydrogenation of CYD was carried out at 1.2 atm of H2 and 30 °C. CYD (0.15 mL, 1.6
mmol) (0.06 mL, 0.63 mmol) was dissolved in a system of [Rh(COD)(PPh3)2]NTf2 (3.2 mg, 3.2
µmol) in one of ionic liquids, [C1C4Im][NTf2] or [C1C1C4Im][NTf2] (1mL), under argon
resulting in red homogeneous solutions. The reaction mixture was kept under hydrogen
143
atmosphere (1.2 atm, constant pressure) until 4 mL of acetonitrile were added to the catalytic
solution. The product distribution in the reaction mixture and the conversion were determined by
GC analyses in presence of toluene as an internal standard. A HP6890 chromatograph equipped
with FID detector and an Al2O3/KCl column (L = 50 m, int = 0.32 mm, film thickness = 5 µm)
was used. Injector and detector temperature were set to 230 °C. Samples were injected in volume
of 1 µL. The temperature of the column was fixed at 190 °C. From those relative response
factors, the mass of each product can be determined by thegeneral formula:
A(x)
A
M(x) = K(x) M(s)
A(s)
A
M(x); mass of product x
K(x); relative response factor of product x
A(x); peak area of product x
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A(s); peak area of standard (butylbenzene)

M(s); mass of standard in the sample (7)
Conversion, yields and mass balance are defined by the following equations, where conversion
of substrates was calculated from unreacted substrates remaining after reaction:
moles of substrate introduced - moles of substrate final
Conv. of substrate =
moles of substrate introduced
moles of product A after reaction - moles of product A introduced
Yield of A =
moles of product after reaction
Mass balance =
3.5.6 Solubility and phase diagrams
Liquid-liquid phase equilibria of the mixture of [C1C4ImNTf2] or [C1C1C4Im][NTf2] and
CYD at atmospheric pressure were determined using a dynamic method with visual detection of
solution turbidity, as already described.49 The mixtures of ionic liquid and CYD at different
compositions were prepared gravimetrically in a glass vial equipped with a stirring bar. First, the
ionic liquid was introduced into a glass vial, then the appropriate amount of CYD was added and
the vial was sealed. In order to minimize the volume of the vapour phase in equilibrium with the
ionic liquid solution and to reduce the error in composition due to differential evaporation, the
glass vial was almost completely filled with the mixture. The uncertainty of the mole fraction is
estimated as ± 0.0001. The cells were then immersed in a thermostatic water bath whose
144
temperature was monitored using a platinum resistance thermometer with a precision of 0.1 K.
The temperature of the bath was first increased slowly until one phase was observed. The clear
homogenous system was then cooled down very slowly (5 K/h) under continuous stirring. The
temperature at which the first sign of turbidity (first cloudiness) appeared was considered as the
temperature of the liquid-liquid phase transition. The overall accuracy in the measurement of
cloud-point temperatures is estimated to be ± 2 K.
3.5.7 Isothermal titration calorimetry
The heat effects resulting from mixing of aliquots of CYD with the ionic liquid were
measured at 303.15 K using an isothermal titration nanocalorimeter equipped with 4 mL glass
cells in a Thermal Activity Monitor TAM III from TA Instruments. An electrical calibration was
done before each experiment and the instrument was chemically calibrated 5 times by titration of
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0.01 M aqueous solution of 18-crown-6 ethers with 0.2 M aqueous solution of BaCl2.
Approximately 2.75 mL of degassed ionic liquid was introduced into 4 mL glass
measuring and reference cells. The liquid in the measuring cell was stirred by a turbine stirrer at
160 rpm and volumes of 4 μL of CYD were injected during 180 seconds using a motor driven
pump (Thermometric 3810 Syringe Pump) equipped with a 100 μL gas-tight Hamilton syringe.
In all experiments, the intervals between consecutive injections were of 35 to 40 minutes, which
provided a good thermal stabilisation of the ionic liquid solution and the return to a stable
baseline. To minimise the undesirable effects of diffusion of the ionic liquid into the canula
linking the CYD syringe to the cell, the canula was immersed in the sample 10 minutes prior the
first injection.
A peak with an area proportional to the resulting heat effect Qi translates to the thermal
effect due to each injection of CYD. The integration of peaks from the recorded calorimetric
plots was performed using the TAM III Assistant software. Each experiment was repeated four
times to obtain reproducible values of Qi at different concentrations within the error bar of ± 2 %.
3.5.8 Density and viscosity
The mixtures of ionic liquid and CYD at different compositions were prepared
gravimetrically following the procedure already described, including the precautions to minimize
vapour head-space.41The viscosity of the mixture was measured at 298.15 K (controlled to within
± 0.005 K and measured with the accuracy better than ± 0.05 K) using a rolling ball viscometer
from Anton Paar, model AMVn, equipped with capillary tubes of 3.0 and 1.8 mm in diameter.
145
Before starting the measurements, the 3.0 mm diameter capillary tube was calibrated as a
function of temperature and angle of measurement with standard viscosity oil from Cannon
(N35). The 1.8 mm diameter tube was calibrated with water by the manufacturer. The overall
uncertainty of the viscosity is estimated as ± 2.0 %.
The densities of the mixtures, necessary to calculate the viscosities were measured in an
Anton Paar vibrating tube densimeter model 512 P, at 298.15 K (measured by a calibrated PRT
with an accuracy of ± 0.02 K). The densimeter was calibrated using n-heptane, bromobenzene
and 2,4-dichlorotoluene. The overall uncertainty of the density is estimated as ± 0.01 %.
3.5.9 NMR spectroscopy
1
H, 13C and 31P solution NMR data were collected at room temperature on a Bruker AC
300 MHz spectrometer with the resonance frequency at 300.130 MHz for 1H nucleus. 103
Rh
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solution NMR was carried out on a Bruker DRX 500 instrument at 298 K (nominal) with a
resonance frequency at 500.130 MHz. The solvent used (CD2Cl2) was distilled and kept in a
rotaflo with molecular sieves. Chemical shifts are reported in ppm (singlet = s, doublet = d,
doublet of doublet = dd, and multiplet = m) and were measured relative to the residual proton of
the solvent to CHDCl2 for 1H, to CD2Cl2 for 13C and to H3PO4 for 31P spectra.
For 1H 1D NMR spectroscopy, the samples with molar ratio R = 0.5 (R is the molar ratio
between the amount of substance of the hydrocarbon and the amount of substance of IL) were
prepared. The mixtures of ionic liquids and hydrocarbon were prepared in closed vials in a glove
box by adding the appropriate amount of CYD to each ionic liquid, [C 1C4Im][NTf2] or
[C1C1C4Im][NTf2]. The resulting systems were stirred for 24 h at 303 K resulting in
homogeneous monophasic solutions. Approximately 0.3 mL of the sample was then introduced
into a 5 mm NMR tube. A stem coaxial capillary tube loaded with CD2Cl2 was inserted into the 5
mm NMR tube to avoid any contact between the deuterated solvent and the analysed mixture.
The deuterium in CD2Cl2 was used for the external lock of the NMR magnetic field and the
residual CHDCl2 in CD2Cl2 was used as the 1H NMR external reference at 5.32 ppm. When 1H
NMR data are obtained in this way, the reference signal of CHDCl2 remains constant and is not
affected by changes in sample concentration.
For ROESY (Nuclear Overhauser Effect SpectroscopY) experiments in the rotating
frame, the 2D sequence was built with the scheme proposed by Bodenhausen (the pulse sequence
shown in Figure 24).64 The mixing time (200 ms) is split into two parts separated by a p-pulse.
146
At each side of the spin lock the B1 field is ramped linearly (4.5 ms) to ensure adiabatic
conditions for spinlock. During the first spinlock pulse, the frequency is shifted to O1 + Df
whereas the second pulse frequency is set to O1 – Df; O1 is the offset frequency and Df set to
give a B1 field at the magic angle. By this way, the ROESY response is roughly constant across
the spectra of interest. 1D sequence, PFGSE (Pulse Field Gradient Spin Echo for Selective
Excitation) have been used and spinlock followed the same scheme as previously.
Figure 24. ROESY pulse sequence.

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Molecules in liquid or solution state move. This translational motion is, in contrast to
rotational motion, known as Brownian molecular motion and is often simply called diffusion or
self-diffusion. It depends on a lot of physical parameters like size and shape of the molecule,
temperature, and viscosity. Assuming a spherical size of the molecule the diffusion coefficient D
is described by the Stokes-Einstein equation (2):
Pulsed field gradient NMR spectroscopy can be used to measure translational diffusion of
molecules and is sometimes referred to as q-space imaging. By use of a gradient, molecules can
be spatially labelled, i.e. marked depending on their position in the sample tube. If they move
after this encoding during the following diffusion time D, their new position can be decoded by a
second gradient. The measured signal is the integral over the whole sample volume and the NMR
signal intensity is attenuated depending on the diffusion time D and the gradient parameters (g,
δ). This intensity change is described by equation (4):
2 2 2
D g
I I 0e (4)
I; the observed intensitu
I0; reference intensity (unattenuated signal intensity)
D; diffusion coefficient
g; gradiant strength
γ; gyromagnetic ratio
δ; length of the gradient
Δ; diffusion time
147
To simplify this equation some parameters are often combined to emphasize the
exponential decay behaviour.
Dq2 ( )
3 DQ
I I 0e or I I 0e (8)
If bipolar gradients are used for dephasing and rephasing a correction for the time t
between those bipolar gradients has to be applied (6).
D 2g 2 2
( / 3 r / 2)
I I 0e (9)
2D DOSY experiments used a slightly modified Bruker experiment ledbpgp2s to improve
lineshape and trapezoidal gradients where implemented for shorter pulses gradients (the pulse
sequences shown in Figure 25). The diffusion evolution time was set to 100 ms, the constant
amplitude part of the gradient was set to 3 ms, and the cosine raising and falling part of gradient
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where set to 150 µs. The diffusion space where sampled by 32 linearly spaced gradients. Values
obtained for D using this technique are tabulated in Tables 4 and 5, as well as viscosity values
and the hydrodynamic radii calculated from these experimental data according to the Stokes-
Einstein relationship (2).
Figure 25. DOSY pulse sequences.

Table 5. The viscosity values η, diffusion coefficients, D, and hydrodynamic radii, rH, calculated from experimental
results, for CYD-[C1C4Im][NTf2] mixtures with varying molar ratio R.
R η [mPa·s] 1/η [mPa- D(CYD) [µm2/s] rH [10-11m]
0 51.02 0.020
0.11 42.39 0.024 91.7 5.52
0.21 36.39 0.027 112.1 5.26
0.34 31.39 0.032 136.9 4.99
0.54 25.93 0.039 183.7 4.50
0.81 21.57 0.046 241.4 4.12
Table 6. The viscosity values η, diffusion coefficients, D, and hydrodynamic radii, rH, calculated from experimental
results, for CYD-[C1C1C4Im][NTf2] mixtures with varying molar ratio R.
R η [mPa·s] 1/η [mPa- D(CYD) [µm2/s] rH [10-11 m]
0.00 107.25 0.009
0.08 86.04 0.012 54.5 4.58
0.18 68.94 0.015 70.4 4.42
0.30 54.90 0.018 88.6 4.41
0.40 47.05 0.021 104.4 4.37
0.69 33.11 0.030 163.4 3.97
148
3.5.10 Molecular simulation

The microscopic structures of the IL-CYD mixtures studied experimentally were also
investigated by molecular simulation, using an atomistic force field that describes interactions
65, 66, 67
and conformations. CYD was represented by the Optimized Potential for Liquid
Simulations force field in its all-atom explicit version (OPLS-AA).68 ILs were represented by a
specifically parameterized force field of the OPLS-AA family in which particular attention was
paid to the description of electrostatic charge distributions and torsion energy profiles. The
OPLS-AA force field is known to reproduce H-bonds well; the electron density of aromatic
systems is represented by the values of electrostatic charges on the relevant atoms that account
for the molecular mutipoles, combined with the Lennard-Jones sites that account for dispersion
interactions. Explicit polarisation of electron clouds is not included in the present model.
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Although this may be important to correctly reproduce dynamic properties of ILs, structural
features and thermodynamic quantities have been described to equivalent levels of accuracy
using fixed-charge models.69
Molecular dynamics simulations of condensed-phase CYD-[C1C4Im][NTf2] and CYD-
[C1C1C4Im][NTf2] mixtures were performed using the DL_POLY program.70 System sizes were
chosen so as to contain about 10000 atoms, and so the numbers of cations, anions and CYD
molecules varied according to composition (e.g. 128 ion pairs and 64 molecules of CYD for
R = 0.5). Initial low-density configurations, with ions and molecules placed at random in
periodic cubic boxes, were equilibrated to attain liquid-like densities and structures at 400 K and
1 bar. Temperature and pressure were maintained using Nosé-Hoover thermostat and barostat,
respectively. Production runs then took 500 ps with an explicit cut-off distance of 16 Å for non-
bonded interactions, and long-range corrections applied for repulsive-dispersive interactions.
Electrostatic energies were calculated using the Ewald summation method with a relative
accuracy of 10-4. Structural quantities such as radial and spatial distribution functions were
calculated from configurations generated during the production runs
149
3.6 References
1. H. Olivier-Bourbigou, L. Magna and D. Morvan, Appl. Catal., A, 2010, 373, 1-56.

2. V. I. Parvulescu and C. Hardacre, Chem. Rev., 2007, 107, 2615-2665.
3. T. Welton, in Multiphase Homogeneous Catalysis, eds. B. Cornils, W. A. Herrmann, I. T.
Horvath, W. Leitner, S. Mecking, H. Olivier-Bourbigou and D. Vogt, Wiley, Weinheim,
2005, pp. 431-454.
4. P. J. Dyson and T. J. Geldbach, Metal Catalysed Reactions in ionic liquid, Springer,
Dordrecht, 2005.
5. J. S. Wilkes, J. Mol. Catal. A, 2004, 214, 11-17.
6. T. Welton, Coord. Chem. Rev., 2004, 248, 2459-2477.
tel-00708600, version 1 - 15 Jun 2012
7. P. J. Dyson, in Comprehensive Coordination Chemistry II, ed. a. M. T. J. Mc Cleverty,

Elsevier, Amsterdam, 2004, pp. 557-566.
8. P. Wasserscheid, in Ionic Liquids in Synthesis, Wiley-VCH, Weinheim, 2003, pp. 213-
257.
9. J. Dupont, G. S. Fonseca, A. P. Umpierre, P. F. P. Fichtner and S. R. Teixeira, J. Am.
Chem. Soc., 2002, 124, 4228-4229.
10. T. Welton, Chem. Rev., 1999, 99, 2071-2083.
11. Chauvin Y., B. Gilbert and I. Guibard, Chem. Commun., 1990, 1715.
12. G. W. Parshall, J. Am. Chem. Soc., 1972, 94, 8716-8719.
13. C. Vallee, C. Valerio, Y. Chauvin, G. P. Niccolai, J.-M. Basset, C. C. Santini, J.-C.
Galland and B. Didillon, J. Mol. Catal. A, 2004, 214, 71-81.
14. Chauvin Y., Mussmann L. and B. H. Olivier, Angew. Chem. Int. Ed., 1995, 34, 2698-
2700.
15. D. Zhao, Z. Fei, T. J. Geldbach, R. Scopelliti and P. J. Dyson, J. Am. Chem. Soc., 2004,
126, 15876-15882.
16. P. Wasserscheid and T. Welton, Ionic liquids in synthesis, Wiley-VCH, Weinheim, 2008.
17. D. J. Cole-Hamilton and R. P. Tooze, Catalyst separation, recovery and recycling:
Chemistry and Process Design, Springer, Dordrecht, 2006.
18. M. Lombardo and C. Trombini, ChemCatChem, 2010, 2, 135-145.
150
19. H. Olivier-Bourbigou, F. Favre, A. Forestiere and F. Hugues, in Handbook of Green

Chemistry: Green Catalysis, ed. P. T. C. Anastas, Robert H., Wiley-VCH, Weinheim,
2009, pp. 101-126. .
20. M. Haumann and A. Riisager, Chem. Rev., 2008, 108, 1474-1497.
21. P. G. Jessop and D. J. Heldebrant, Environ. Catal., 2005, 627-648.
22. H. Olivier-Bourbigou and C. Vallee, in Multiphase Homogeneous Catalysis, Wiley-VCH,
Weinheim, 2005, pp. 413-431.
23. C. J. Mathews, P. J. Smith and T. Welton, J. Mol. Catal. A, 2004, 214, 27-32.
24. H. Lebel, M. K. Janes, A. B. Charette and S. P. Nolan, J. Am. Chem. Soc., 2004, 126,
5046-5047.
25. S. P. Nolan and N-Heterocyclic Carbenes in Synthesis, Wiley-VCH, Weinheim., 2006.
tel-00708600, version 1 - 15 Jun 2012
26. L. Magna, Y. Chauvin, G. P. Niccolai and J.-M. Basset, Organometallics, 2003, 22,
4418-4425.
27. V. Lecocq and H. Olivier-Bourbigou, Oil & Gas Sci. Tech, 2007, 62, 761-773.
28. U. Hintermair, T. Gutel, A. M. Z. Slawin, D. J. Cole-Hamilton, C. C. Santini and Y.
Chauvin, J. Organometal. Chem., 2008, 693, 2407-2414.
29. J. A. Boon, J. A. Levisky, J. L. Pflug and J. S. Wilkes, J. Org. Chem., 1986, 51, 480-483.
30. A. Mele, G. Romano, M. Giannone, E. Ragg, G. Fronza, G. Raos and V. Marcon, Angew.
Chem. Int. Ed., 2006, 45, 1123-1126.
31. A. Triolo, O. Russina, H.-J. Bleif and E. Di Cola, J. Phys. Chem. B, 2007, 111, 4641-
4644.
32. A. Triolo, O. Russina, B. Fazio, G. B. Appetecchi, M. Carewska and S. Passerini, J.
Chem. Phys., 2009, 130, 164521/164521-164521/164526.
33. J. Fuller, R. T. Carlin, H. C. De Long and D. Haworth, J. Chem. Soc., Chem. Commun.,
1994, 299-300.
34. C. Hardacre, J. D. Holbrey, S. E. J. McMath, D. T. Bowron and A. K. Soper, J. Chem.
Phys., 2003, 118, 273-278.
35. J. N. A. Canongia Lopes and A. A. H. Padua, J. Phys. Chem. B, 2006, 110, 3330-3335.
36. Y. Wang, S. Izvekov, T. Yan and G. A. Voth, J. Phys. Chem. B, 2006, 110, 3564-3575.
40, 1087-1096.
151
38. A. E. Bradley, C. Hardacre, J. D. Holbrey, S. Johnston, S. E. J. McMath and M.

Nieuwenhuyzen, Chem. Mater., 2002, 14, 629-635.
110, 16816-16818.
40. J. Lachwa, I. Bento, M. T. Duarte, J. N. C. Lopes and L. P. N. Rebelo, Chem. Commun.,
2006, 2445-2447.
41. T. Gutel, C. C. Santini, A. A. H. Padua, B. Fenet, Y. Chauvin, J. N. Canongia Lopes, F.
Bayard, M. F. Costa Gomes and A. S. Pensado, J. Phys. Chem. B, 2009, 113, 170-177.
42. A.-L. Revelli, F. Mutelet and J.-N. Jaubert, J. Phys. Chem. B, 2010, 114, 4600-4608.
43. D. Xiao, L. G. Hines, Jr., R. A. Bartsch and E. L. Quitevis, J. Phys. Chem. B, 2009, 113,
4544-4548.
tel-00708600, version 1 - 15 Jun 2012
44. T. Umecky, Y. Saito and H. Matsumoto, J. Phys. Chem. B, 2009, 113, 8466-8468.
45. T. Umecky, Y. Saito and H. Matsumoto, ECS Transactions, 2010, 25, 23-29.
46. M. A. Vorotyntsev, V. A. Zinovyeva and M. Picquet, Electrochim. Acta 2010, 55, 5063-
5070.
47. V. Kempter and B. Kirchner, J. Mol. Struct., 2010, 972, 22-34.
48. P. A. Hunt, J. Phys. Chem. B, 2007, 111, 4844-4853.
49. M. Blesic, J. N. Canongia Lopes, A. A. H. Padua, K. Shimizu, M. F. Costa Gomes and L.
P. N. Rebelo, J. Phys. Chem. B, 2009 113, 7631.
50. U. Domańska, Z. Żołek-Tryznowska and M. Królikowski, J. Chem. Eng. Data, 2007, 52,
1872.
51. W. Marczak, S. P. Verevkin and A. Heintz, J. Solution Chem., 2003, 32, 519-526.
52. I. Natori, K. Imaizumi, H. Yamagishi and M. Kazunori, J. Polym. Sci. B 1998, 36, 1657.
53. D. Frezzato, F. Rastrelli and A. Bagno, J. Phys. Chem. B, 2006, 110, 5676-5689.
54. M. Clark, R. D. Cramer, III and N. Van Opdenbosch, J. Comp. Chem., 1989, 10, 982-
1012.
55. W. Sutherland, Philos. Mag., 1905, 781.
56. R. R. Schrock and J. A. Osborn, J. Am. Chem. Soc., 1976, 98, 4450-4455.
57. R. R. Schrock and J. A. Osborn, J. Am. Chem. Soc., 1976, 98, 2134-2143.
58. P. W. N. M. Van Leeuwen, Homogeneous Catalysis Understanding the art, Kluwer,
Dordrecht, 2004.
152
59. J. Jacquemin, M. F. Costa Gomes, P. Husson and V. Majer, J. Chem. Thermodyn., 2006,
38, 490-502.
60. J. Jacquemin, P. Husson, V. Majer and M. F. Costa Gomes, Fluid Phase Equilib., 2006,
240, 87.
61. M. F. Costa Gomes, J. Chem. Eng. Data, 2007, 52, 472-475.
62. W. Shi, D. C. Sorescu, D. R. Luebke, M. J. Keller and S. Wickramanayake, J. Phys.
Chem. B, 2010, 114, 6531-6541.
63. K. Ueno, H. Tokuda and M. Watanabe, Phys. Chem. Chem. Phys. , 2010, 12, 1649-1658.
64. B. Cutting, R. Ghose and G. Bodenhausen, J. Magn. Reson., 1999, 138, 326-329.
65. J. N. Canongia Lopes, J. Deschamps and A. A. H. Pádua, J. Phys. Chem. B, 2004, 108,
2038-2047.
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66. J. N. Canongia Lopes and A. A. H. Pádua, J. Phys. Chem. B, 2004, 108, 16893-16898.
67. J. N. Canongia Lopes, A. A. H. Padua and K. Shimizu, J. Phys. Chem. B 2008, 112,
5039-5046.
68. W. L. Jorgensen, D. S. Maxwell and J. Tirado-Rives, J. Am. Chem. Soc., 1996, 118,
11225-11236.
69. E. J. Maginn, Acc. Chem. Res., 2007, 40, 1200-1207.
70. W. Smith, T. R. Forester and I. T. Todorov, ed. T. D. P. m. s. package, STFC Daresbury
Laboratories, , Warrington , UK, 2007, p. The DL_POLY molecular simulation package.
153
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154
IV
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Chapter 4
Nanoparticle Catalysis in
Imidazolium Ionic Liquids
The influence of size on catalytic

performance
155
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156
Chapter 4 NP catalysis in Imidazolium ILs – The influence of size on catalytic performance
Chapter 4
Nanoparticle Catalysis in Imidazolium Ionic Liquids

The influence of size on catalytic performance
4.1 Introduction .................................................................................................................................. 159
4.1.1 The influence of size on activity.............................................................................................. 159

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4.1.2 The influence of size on selectivity ......................................................................................... 160
4.2 Catalyst synthesis and characterisation ........................................................................................ 161
4.2.1 TEM......................................................................................................................................... 161
4.2.2 X-ray photoelectron spectroscopy ........................................................................................... 163
4.2.3 Rus concentration ..................................................................................................................... 164
4.3 Substrate....................................................................................................................................... 165
4.3.1 Solubility ................................................................................................................................. 165
4.3.2 Viscosity .................................................................................................................................. 166
4.4 Catalysis mixture preparation ...................................................................................................... 167
4.5 Influence of NP size on catalytic activity .................................................................................... 168
4.5.1 1,3-cyclohexadiene .................................................................................................................. 168
4.5.2 Cyclohexene ............................................................................................................................ 168
4.5.3 Limonene ................................................................................................................................. 169
4.5.4 Styrene ..................................................................................................................................... 170
4.5.5 Comparison of the substrates ................................................................................................... 170
4.6 Influence of NP size on catalytic selectivity ................................................................................ 171
4.6.1 1,3-cyclohexadiene .................................................................................................................. 171
157
4.6.2 Limonene ................................................................................................................................. 173
4.6.3 Styrene ..................................................................................................................................... 175
4.7 Hydrogen effect ........................................................................................................................... 177
4.8 Recycling ..................................................................................................................................... 178
4.9 Conclusion ................................................................................................................................... 180
4.10 Outlooks ....................................................................................................................................... 181
4.11 Experimental section.................................................................................................................... 182
4.11.1 Materials and methods ........................................................................................................ 182
4.11.2 Catalysts synthesis .............................................................................................................. 182
4.11.3 Determination of particle size by TEM ............................................................................... 182

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4.11.4 X-ray Photoelectron Spectroscopy (XPS) ........................................................................... 183
4.11.5 Catalytic tests ...................................................................................................................... 183
4.11.6 Product quantification ......................................................................................................... 184
4.11.7 GC-MS ................................................................................................................................ 184
4.11.8 Density and viscosity .......................................................................................................... 184
4.11.9 Solubility ............................................................................................................................. 184
4.12 References .................................................................................................................................... 185
158
4.1 Introduction
Transition metal nanoparticles (NPs) of 1–10 nm in size exhibit physical-chemical

properties intermediate to those of the smallest element from which they can be composed and
those of the bulk material.1-3 In catalysis, the performance (activity and selectivity) of NPs is
often said to be related to their size, as this controls the number of corner, edge and face atoms
available for adsorption and activation of substrates.4-9
For example, depicted in Figure 1 are crystalline NPs of a face centred cubic crystal
structure adopting a truncated octahedral shape. A given substrate will coordinate differently to
each of the different sites labelled. The relative numbers of each site varies with the size of the
NPs, hence the reactivity varies.
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Figure 1. Simplified model of NPs of metals adopting an fcc crystal lattice.
4.1.1 The influence of size on activity

First of all, the catalytic activity may be related to the size. For example, a study of
ammonia synthesis over Fe single crystals found an increase in turnover frequency, TOF, with
159
increasing size, which was attributed to the greater availability of the (111) face, the most active
site for this reaction.10 The activity in CO hydrogenation of supported RhNPs with hcp structure
has been found to increase drastically with NP size, due to the larger number of steps on the
11
surface. In contrast, in ethane hydrogenolysis to methane over Pt nanoparticles, the turnover
rate has been shown to decrease with particle size while activation energy increases, indicating
that the more unsaturated vertex and/or edge positions are responsible for activity.12
4.1.2 The influence of size on selectivity
When several different products are possible, selectivity becomes an important issue.
This has been shown to vary with particle size. For instance, the hydrogenation/dehydrogenation
of cyclohexene over PtNPs has been shown to exhibit size-dependent selectivity, smaller NPs
favouring benzene production, Figure 2.13
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Figure 2. The size dependence of Pt nanoparticles on the selectivity of cyclohexene

hydrogenation/dehydrogenation.
Furthermore, it has also been reported in a study of the hydrogenation of benzene over Pt,
that on the (111) face cyclohexane and cyclohexene are produced, whereas on the (100) face
only cyclohexene is produced. This result implies that cubic NPs, exhibiting uniquely (100)
faces, would produce selectively cyclohexene in the hydrogenation of benzene.6, 13
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From the results mentioned above and many more examples in the literature,6 it is clear
that the size of NPs can be a deciding factor in catalytic processes. Nonetheless, the synthesis of
nanoparticles (NPs) with a controlled size in the range of 1–10 nm in order to corroborate this
theory is a challenging issue.14 The aim of this chapter is to use the ionic liquid route to
synthesise catalytically active RuNPs of distinct and controlled sizes, and thus investigate
thoroughly the consequences of changing NP size on the catalytic process, in particular
hydrogenation.
4.2 Catalyst synthesis and characterisation

It has been previously demonstrated that the size of RuNPs generated from the
decomposition of ( 4-1,5-cyclooctadiene)( 6-1,3,5-cyclooctatriene)ruthenium(0),
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[Ru(COD)(COT)] under H2, may be governed by the degree of self-organisation of the

imidazolium based ionic liquid in which they are formed: the more structured the ionic liquid,
the smaller the size.15 In the same IL, the organisation and structure may be altered by simply
altering the experimental conditions, i.e. temperature and stirring. Therefore, following these
principles and previously described methods, RuNPs were synthesised at 0 °C, 25 °C, 50 °C and
75 °C in an attempt to obtain a selection of mono-disperse sizes of RuNP in the same IL. The IL
chosen is 1-butyl-3-methylimidazolium bis(trifluorosulphonyl)imide, [C1C4Im][NTf2].
4.2.1 TEM
Analysis of the suspensions obtained by transition electron microscopy, TEM, allowed
determination of the sizes obtained; 1.1 ± 0.2 nm, 2.3 ± 0.3 nm, 2.9 ± 0.4 nm and 3.1 ± 0.7 nm,
for RuNPs generated at 0 °C (Ru0), 25 °C (Ru25), 50 °C (Ru50) and 75 °C (Ru75), respectively,
Figure 3. As can be seen from the TEM image of Ru75 and the consequent size distribution
histogram, Figure 4, the size of these NPs does not vary significantly compared to those of Ru 50
although a poorer size control (wider distribution) is apparent. For this reason, these NPs are not
used in catalytic tests. High resolution electron microscopy, HREM, revealed the crystalline
nature of the RuNPs formed through elucidation of the crystal planes. For Ru0, only a larger NP
of ≈ 2 nm was observed by HREM, probably due to the difficulty in observing the smallest NPs
with limited contrast, although this may be indicative of a lower degree of crystallinity in very
small RuNPs, as already observed by reverse Monte Carlo simulations.16
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2 nm
5 nm
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5 nm
Figure 3. Transition electron micrograph of RuNPs and high resolution electron micrograph examples showing
crystallinity for Ru0 (top left), Ru25 (top right), Ru50 (bottom left) and Ru75 (bottom right).
162
160
140 T = 0 °C
T = 25 °C
120
T = 50 °C
100 T = 75 °C
Frequency 80
60
40
20
0
1 2 3 4 5
Size/ nm
Figure 4. Size distribution histograms for RuNPs prepared in [C1C4Im][NTf2] at different temperatures.
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4.2.2 X-ray photoelectron spectroscopy

In order to establish the oxidation state of the RuNPs, X-ray photoelectron spectroscopy,
XPS, was performed. Due to the weak concentration of the solution and the fact that the only
photoelectrons from a maximum depth of 10 nm may be detected, no peaks corresponding to Ru
binding energies were observed when the analyses were carried out directly on the RuNP/IL
solutions. Samples were therefore prepared by filtering the RuNPs onto silica under inert
atmosphere and eliminating as much IL as possible. The resulting spectra of the Ru 3p region are
depicted in Figure 5. It is clear that in each case, fine peaks are observed, indicating the presence
of only one Ru species. The low 3p3/2 binding energy observed in each case, 460.3 eV, and
doublet separation of 22.2 eV correspond closely to metallic zero-valent ruthenium, often
reported with a 3p3/2 binding energy of around 461 eV.17 The small difference may be attributed
to the presence of small crystallites, which tend to exhibit lower binding energies than bulk
metal. Indeed, as recently shown for AuNPs,18 the d-band narrows with decreasing particle size
and shifts towards the Fermi level.
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Figure 5. XPS spectra of the Ru 3p region after NP filtration onto SiO2, experimental data and fitted peaks.
Left Ru0, middle Ru25 and right Ru50.
4.2.3 Rus concentration

In order to investigate uniquely the effect of changing NP size on catalysis all other
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variables must remain unchanged. Therefore maintaining constant the initial ratio of substrate to
catalyst is imperative. In NP catalysis, as in heterogeneous catalysis, only the atoms at the
surface (Rus) take part in reaction. The dispersion (D) presents the ratio between surface atoms,
Rus and the total number of atoms, RuT (D = Rus/RuT) and varies with the size of the NPs,
smaller particles of course having a larger percentage of surface atoms. The different dispersion
values must therefore be taken into account for each size of nanoparticle formed.
Ruthenium is known to exhibit a hexagonal close-packed crystal structure, with the
following lattice parameters: a: 270.59 pm b: 270.59 pm c: 428.15 pm α: 90° β: 90° γ: 120°.19
Using these parameters, SYBYL software can be applied to extrapolate the lattice until the
measured diameters, in order to model the structure of the different size NPs, assuming
crystallinity. It is seen that crystalline hexagonal close-packed RuNPs would adopt a truncated
hexagonal bipyramid form, with two symmetric hexagonal faces (0001) and twelve irregular and
uneven trapezoid faces (10 –11).20 From these findings a curve of D with respect to diameter can
be plotted and then used to estimate D for each size of nanoparticle, Figure 6.
164
100%
90%
80%
70%
60%
Dispersion
50%
40%
30%
20%
Dispersion = 0.8622 Diameter-0.63
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10%
0%
0 0.5 1 1.5 2 2.5 3 3.5
Diameter / nm
Figure 6. Curve of dispersion against mean diameter of crystalline hcp RuNPs.
4.3 Substrate
The substrate principally investigated is the conjugated diene, 1,3-cyclohexadiene

(CYD). It has been shown that in ionic liquid media CYD may be partially hydrogenated with
high selectivity by molecular catalysts due to the reduced miscibility of cyclohexene (CYE) in
the medium.21-23 Full hydrogenation would lead to cyclohexane (CYA), Scheme 1.
Scheme 1. 1,3-cyclohexadiene and its hydrogenation products.

4.3.1 Solubility
The solubilities of the substrate and potential products may play an important role in the
activity and/or selectivity of the system. For example, selective hydrogenation of butadiene to
butenes has been performed by Dupont’s group in ionic liquids due to the difference in solubility
165
of the partially hydrogenated product.24 The same group has also described the possibility of
extracting cyclohexene during benzene hydrogenation using this solubility difference. 25 For this
reason, solubilities of CYD, CYE and CYA were measured. It was found that the solubility of
the hydrogenated products (6 ± 1 % wt - CYE, 4 ± 1 % wt- CYA) is much lower than that of
CYD (12 ± 2 % wt), therefore the medium may tend to a biphasic system during the course of
the reaction. As a result, the collection of aliquots from a single batch would render inaccurate
results. Consequently, each measure of conversion recorded in this work, hence each point
plotted, corresponds to a separate experiment, quenched after time t by opening the reaction
vessel to air, thus releasing the hydrogen, and dissolving the catalytic system entirely in a 1
molar solution of toluene in acetonitrile for gas phase chromatography.
4.3.2 Viscosity
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Thermophysical properties of the reaction medium such as density and viscosity may also
influence the catalytic performance. As demonstrated in Chapter 3, and by others, reaction
kinetics in IL media are highly dependent on the mobility of molecules.21,26-28 Furthermore,
knowledge of the viscosity is very important from engineering point of view as it plays a major
role in stirring, mixing and pumping processes. Consequently, identical concentrations of
substrate must be used in each case in order to maintain constant viscosity and eliminate effects
due to mass transport. The densities and viscosities of the pure [C1C4Im][NTf2] and that of the
mixtures with CYD were measured at different molar ratio CYD/IL (R) at 25 °C and atmospheric
pressure. The results are presented in Table 1.
Table 1. Density, ρ, and viscosity, η, of CYD-IL mixtures of different compositions at 298 K and atmospheric
pressure. xIL= molar fraction of IL, R = molar ratio CYD/IL
R xIL ρ/g cm-3 η/mPa s
0.000 1.000 1.4376±0.0001 48.5±0.4
0.100 0.909 1.4202±0.0001 44±1
0.200 0.833 1.3999±0.0001 37.0±0.4
0.300 0.769 1.3874±0.0003 33.3±0.3
0.397 0.716 1.3718±0.0001 31.0±0.3
0.498 0.667 1.3597±0.0001 24.8±0.3
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As can be seen, the viscosity of the mixtures of CYD in IL varies greatly with the
concentration of CYD. From the Stokes-Einstein equation, the diffusion coefficient, D, which
reflects the mobility of molecules, varies inversely with η, equation (1), see Chapter 3.
kT
D (1)
rH
For the purpose of our investigations the concentration of CYD is fixed at 10 % wt.
(corresponding to a molar ratio R = 0.59), which is lower than the limit of solubility, limiting
phenomena due to formation of a biphasic system. According to results reported in Chapter 3, a
molar ratio of R = 0.59 gives a perfectly “sticking” medium for which the Stokes-Einstein
equation (1) is followed with the Sutherland coefficient, = 6.
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4.4 Catalysis mixture preparation
Table 2. Calculations for the composition of the catalytic systems. Column 1- Name of catalyst, Column 2- Average
RuNP diameter measured by TEM, Column 3- Calculated dispersion, Column 4- Initial Ru(COD)(COT)
concentration, Column 5- Consequent Rus concentration, Column 6- Volume of IL/RuNP solution ,Column 7-
Volume of pure IL added, Column 8- Consequent number of moles of Rus in the 5 mL mixture, Column 9- mass of
IL, Column 10- mass of substrate, Column 11- Substrate-Catalyst ratio, Column 12- Substrate-IL ratio.
1 2 3 4 5 6 7 8 9 10 11 12
Vol. IL- Vol.

[Ru]/ [Rus]/ Ru s / m m
IL
RuNP
d/nm D mmol mmol pure/ 10-5 IL/ CYD/ CYD/Rus CYD/IL
solution/
L L moles g g
mL
mL
Ru0 1.1 82% 43.0 35.2 2.42 2.58 9.52 7.0 0.78 105 0.59
Ru25 2.3 53% 43.0 22.9 3.74 1.26 9.52 7.0 0.78 105 0.59
Ru50 2.9 43% 43.0 18.5 5.00 - 9.52 7.0 0.78 105 0.59
In Table 2, are collected all data concerning the hydrogenation of CYD. In columns 1-3,
size and dispersion values of (Ru0), (Ru25), (Ru50) are reported. Given the concentration of NP
precursor (column 4) and the size of NPs generated (column 2), it is possible to calculate the
concentration of Rus for Ru0, Ru25 and Ru50 (column 5). The more concentrated solutions of Rus
(Ruo and Ru25) can be easily diluted to match the least concentrated (Ru50) by simple addition of
the appropriate amount of pure IL (columns 6 and 7), resulting in identical quantities of Ru s
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(column 8). Identical concentrations of substrate may then be used, below the limit of solubility
to avoid demixing (10 % wt) (columns 9 and 10), permitting as a result both a constant substrate-
catalyst ratio (column 11) and a constant substrate-IL ratio (column 12) hence constant viscosity.
Using solutions prepared as described, the reaction was carried out in parallel in several
0.5 mL batches under 1.2 bars of pure molecular hydrogen, which were stirred and heated with
the aid of a thermostatic carousel, ensuring identical reaction conditions.
4.5 Influence of NP size on catalytic activity
4.5.1 1,3-cyclohexadiene
It can be seen in Table 3 that the largest NPs (2.9 nm) are the most active in the
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hydrogenation of CYD, activity decreasing with decreasing size.
Table 3. Conversion and selectivity for the hydrogenation of CYD

Pressure H2 / Conversion at Selectivity
TON TOF / h-1
bar 90min CYE
Ru0 (1.1 nm) 1.2 66±5 % 97 % 70±5 46± 3
Ru25 (2.3 nm) 1.2 75±5 % 86 % 79±5 53± 3
Ru50 (2.9 nm) 1.2 83±5 % 80 % 87±5 58± 3
In a similar fashion, the three sizes of RuNP were tested in the catalytic hydrogenation of
other substrates to determine whether this size-related activity could be generalised.
4.5.2 Cyclohexene
To establish whether or not a difference in activity is also apparent in the case of a
monoene, the hydrogenation of cyclohexene (CYE) to cyclohexane (CYA) was studied. The
results tabulated in Table 4 show that the larger NPs are indeed more active, however the
difference in activity is less substantial than in the case of the conjugated diene CYD, and falls
within experimental error.
168
Table 4. Conversion for the hydrogenation of CYE

Conversion at 90min TON TOF / h-1
Ru0 (1.1 nm)

61± 5 % 64± 5 43± 3
Ru25 (2.3 nm)
64± 5% 67± 5 45± 3
Ru50 (2.9 nm)
67± 5 % 70± 5 47± 3
4.5.3 Limonene
The naturally occurring terpene, (R)-(+)-limonene, or 1-methyl-4-isopropenyl-1-
cyclohexene, Lim, was also chosen as a substrate. This molecule is also a non-conjugated diene
as can be seen in Scheme 2.
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Scheme 2. (R)-(+)-limonene.
Kinetic tests for the hydrogenation of Lim were carried out in the same way as those for
CYD, using this time only 5 % wt. of substrate with respect to the IL, due to its lower solubility
in the medium. Mixture compositions are given in Table 5.
Table 5. Compositions of the catalytic systems for the hydrogenation of limonene and conversion after 120 minutes
Conversion
Vol.
[Ru]/ [Rus]/ Vol. IL- Ru s /
IL mass
RuNP mass at 120
d/nm D mmol mmol solution/ pure/ 10-5 Lim/ Lim/Rus Lim/IL
IL/ g mins
g
L-1 L-1 mL moles
mL %
Ru0 1.1 82% 43.0 35.2 2.42 2.58 9.52 7.0 0.37 28 0.16 90%
Ru25 2.3 53% 43.0 22.9 3.74 1.26 9.52 7.0 0.37 28 0.16 88%
Ru50 2.9 43% 43.0 18.5 5.00 - 9.52 7.0 0.37 28 0.16 92%
At 30 °C, after 2 hours of reaction ~ 90 % of Lim was converted in each case, Table 5.
Here, no remarkable difference in activity is apparent.
169
4.5.4 Styrene
The hydrogenation of styrene, Sty, affords either a partially (ethylbenzene, EBn) or fully
hydrogenated product (ethylcyclohexane, ECYA) (Scheme 3). Generally, the hydrogenation of
the olefinic position is faster than the aromatic ring.
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Scheme 3. The possible products from the hydrogenation of styrene.
As for CYD, CYE and Lim, kinetic tests for the hydrogenation of Sty were carried out
using the three differently sized RuNPs produced in the ILs. Mixture compositions and
conversions are given in Table 6.
Table 6. Compositions of the catalytic systems for the hydrogenation of styrene and conversion after 120 minutes.
Vol. IL- Vol.
[Ru]/ [Rus]/ Ru s / mas Conversion
d/ RuNP IL mass Sty Sty/
D mmol mmol 10-5 s IL/ at 120
nm solution/ pure/ Sty/ g /Rus IL
L-1 L-1 moles g mins%
mL mL
Ru0 1.1 82% 43.0 35.2 2.42 2.58 9.52 7.0 0.78 81 0.45 60 %
Ru25 2.3 53% 43.0 22.9 3.74 1.26 9.52 7.0 0.78 81 0.45 60 %
Ru50 2.9 43% 43.0 18.5 5.00 - 9.52 7.0 0.78 81 0.45 63 %
At 30 °C, the hydrogenation of the external double bond in each case was rapid, leading
to 70 % conversion after 2 h in all cases. Selectivity for EBn remained at 100% for all sizes of
NP. As was the case for limonene and CYE, at 30 °C, no significant size effect was observed.
4.5.5 Comparison of the substrates
According to literature results, the catalytic activity of NPs depends on their size, and
generally reaches a maximum for those of around 3 nm.29,30 Here, only a size effect on activity
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was observed for the case of CYD. The fact that the hydrogenation of CYD is faster with larger
NPs can be related to two factors:
1) Larger NPs present the appropriate number of neighbouring surface sites to facilitate
the -bond activation of the conjugated system.31
2) Through this -bonding activation, similarly to benzene, 1,3-cyclohexadiene would
lose part of its resonance energy and react more readily.20
The coordination of monoenes such as CYE or the olefinic bond of styrene does not
necessitate large surfaces, explaining the less pronounced size effect in these cases.
In the case of limonene, unlike in CYD, the double bonds are not conjugated and so a
planar π-coordination to disrupt conjugation is not energetically advantageous, hence the result is
similar to that of a monoene.
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4.6 Influence of NP size on catalytic selectivity
4.6.1 1,3-cyclohexadiene
100%
1.1 nm
95%
2.3 nm
Selectivity for CYE
90% 2.9 nm
85%
80%
75%
70%
0% 20% 40% 60% 80% 100%
Conversion
Figure 7. Selectivity for cyclohexene as a function of conversion for the three different sizes of RuNPs
171
In the hydrogenation of CYD, CYE is obtained as the major product. Interestingly, the
selectivity for CYE diminishes with increasing NP size. Indeed, in the case of Ru0, selectivity for
CYE is 100% at low conversion and only slightly diminishes at high conversion (97%). In
contrast, for Ru50 the hydrogenation is unselective even at low conversion (Figure 7).
Assuming highly crystalline particles with hcp structure, a particle of diameter 1.1 nm
would have the vast majority of catalytic surface atoms occupying vertex or edge positions. Such
vertex ruthenium atoms Ruv, which under H2 atmosphere are ligated by hydrides,32 may
coordinate one C=C double bond of CYD. The product of the subsequent hydrogenation is CYE,
which must undergo a second coordination to give the fully hydrogenated CYA. Similarly, for a
larger particle of average diameter 2.9 nm assuming high crystallinity and a hcp structure, it is
evident that most of the catalytically active surface ruthenium atoms are found in facial
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positions, Ruf. Indeed, here such crystallinity has already been observed by HREM, Figure 1. Ruf
may hydrogenate the olefin using the mechanism previously discussed, but due to the planar
arrangement of Ruf, another mechanism may be envisaged involving the double coordination of
the diene, as generally found during the hydrogenation of 1,3-cyclohexadiene on metallic
surfaces,33,34 and thus rapid consecutive or simultaneous hydrogenation of both double bonds
leading to the fully hydrogenated CYA may be possible. In Figure 8 are represented simplified
SYBYL models of CYD molecules coordinating to the surface of perfectly crystalline RuNPs of
calculated average diameter 1.3 nm and 2.8 nm. This illustrates nicely the greater facility of
planar coordination to faces of the larger NPs. Through this -bonding activation similarly to
benzene, 1,3-cyclohexadiene would lose part of its resonance energy and react more readily. This
could explain the lower selectivity of the larger RuNPs despite identical reaction conditions.
Likewise, in the hydrogenation of 1,3-butadiene or 1-hexyne the selectivity of small NPs towards
1-butene or 1-hexene versus butane or hexane is still higher than that of larger NPs.31, 33-35 In this
work, in the hydrogenation CYD the selectivity in CYE versus CYA drops from 97% to 80%
when the RuNP size increases from 1.1 to 2.9 nm.
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Figure 8. SYBYL representations of CYD coordinated to the face of highly crystalline RuNPs of mean diameter
1.3 nm (left) and 2.8 nm (right)
4.6.2 Limonene
Limonene, containing two double-bonds, both inside and outside of the cyclohexene ring,
may also yield different products, as depicted in Scheme 4. Complete hydrogenation would yield
mixture of cis- and trans-p-menthane, c and d, whereas partial hydrogenation may result in one
of the intermediates p-1-menthene or 1-methyl-4-isopropenylcyclohexane, a and b. Several
groups have reported however, that hydrogenation of the external double bond is preferential, so
only p-1-menthene is detected as a partially hydrogenated product of this reaction.36
173
Scheme 4. The possible products resulting from the hydrogenation of limonene.
When the catalytic hydrogenation was performed at 30 °C, high selectivity for the
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partially hydrated product menthene was observed, although both menthanes are formed slowly
over time. As for CYD hydrogenation the selectivity was the poorest in the case of Ru50. Unlike
for CYD, 100% selectivity is only observed at very low conversion (≤ 20 %) with Ru0 (Figure
9).
Figure 9. Selectivity for p-1-menthene at 30°C as a function of conversion for the three different sizes of RuNPs.
In an attempt to increase the selectivity, the same reaction was therefore performed at low
temperature (-2 °C). For all sizes of nanoparticle, the selectivity for menthene is increased
174
compared to when carried out at ambient temperature. Interestingly the trend of selectivity
although poor at the start of the reaction improved between 10 – 20 % conversion, Figure 10.
This phenomenon must be due to the start of a biphasic system, thus leading to extraction of the
product, inducing a better selectivity as already reported in the hydrogenation of butadiene to
butenes,24 and benzene to cyclohexene.25
For the hydrogenation of limonene which contains two non-conjugated double-bonds, the
selectivity is NP size-dependent at 30 °C, 100 % selectivity for p-1-menthene being observed at
low conversion for the smallest NPs. At -2 °C, decreasing the solubility of both substrate and
products affords a higher selectivity in all cases, mainly due to the formation of biphasic media.
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Figure 10. Selectivity for p-1-menthene at -2 °C as a function of conversion for the three different sizes of RuNPs.
4.6.3 Styrene
It is often reported that the activity and the selectivity in aromatic hydrogenation are size
and face dependant.4,6,13
A common probe for chemo-selectivity in the hydrogenation of aromatics is styrene, Sty.
Generally, the hydrogenation of the olefinic double bond is faster than the aromatic ring and
occurred at 30 °C with 100 % selectivity for EBn, vide supra. This is because a greater energy
barrier must be overcome when hydrogenating an aromatic compared to an olefin. Therefore to
175
force the hydrogenation of the aromatic ring, the same reaction must be carried out at higher
temperature and for a longer duration, here 75 °C during a period of 6 h.
Once again, the hydrogenation of the external double bond was rapid and occurred
quantitatively for each size of NP, Figure 11. Only at 100 % conversion was hydrogenation of
the aromatic cycle observed, indicating a successive hydrogenation of the different functions.
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Figure 11. Hydrogenation of Sty at 75 °C under 1.2 bar H2 in [C1C4Im][NTf2], for three different sized RuNPs.
In Figure 12 is depicted the yield in ECHA with respect to time. Here it can be clearly
seen that the full hydrogenation of the aromatic occurs more readily on the large NPs, in
agreement with results for the hydrogenation of CYD. Here, a planar coordination is even more
crucial, as the inert aromatic ring must lose part of its resonance energy to be activated.20
Using styrene as a probe has emphasised the importance of planar π-coordination in
aromatic hydrogenation as the larger NPs fully reduced styrene to ethylcyclohexane more readily
than the smaller NPs
176
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Figure 12. Hydrogenation of Sty at 75°C under 1.2 bar H2 in [C1C4Im][NTf2], for three different sized RuNPs.
It is also interesting to note that during the course of the reaction small amounts of 1-
ethylcyclohexene were produced, and identified by GC-MS: as much as 0.5 % for Ru0, by the
end of the reaction. Indeed the partial hydrogenation of aromatic cycles is an interesting and
ongoing challenge and has already been reported in IL media for benzene.25 It may be interesting
in the future to optimise conditions to favour the production and extraction of this molecule from
the medium.
4.7 Hydrogen effect

Increasing H2 pressure to 4 bars in the case of Ru0 and Ru50 is seen to affect neither the
activity nor selectivity in a substantial manner, Table 7. It is generally reported that a higher H2
concentration should not influence the activity of the small particles as the H2 storage capacity is
related to the particle volume and only large particles may experience an increase in availability
of subsurface hydrogen.30 In reality, a slight decrease in activity is observed, possibly indicating
that it is the slight enhancement in viscosity with the increase in pressure that controls the
mobility of the reactants.37 This proves that the rate is not dictated by the availability and
177
adsorption of H2, in agreement with observations of labile surface hydrides on the NP surface,32
but the mobility and absorption of the substrate.21
Table 7. Results for the catalytic hydrogenation of CYD using Ru 0 and Ru0 under 1.2 bars and 4 bars H2
Pressure H2 / Conversion at 90 Selectivity
TON TOF / h-1
bar min CYE
Ru0 (1.1 nm) 1.2 66 % 97 % 70 46
Ru50 (2.9 nm) 1.2 83 % 80 % 87 58
Ru0 (1.1nm) 4.0 57% 92% 59 40
Ru50 (2.9 nm) 4.0 73% 80% 77 51
4.8 Recycling
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TEM images of the reaction media after hydrogenation of CYD show a reorganisation of
the NPs, probably due to the presence of organic substrates, poorly soluble in the IL. For Ru0 and
Ru25, circular patterns are present, possibly caused by the formation of aggregates, where the
NPs would decorate the organic-IL interface Figure 13. In the case of Ru50 phase separation is
apparent, which may be indicative of a larger amount of CYE and CYA present as a result of the
higher activity and lower selectivity. In all cases, the mean RuNP size measured Table 8 does not
differ greatly from the original size, in accordance with the stability of RuNPs in ILs under
molecular hydrogen,32 however the size distribution is larger, probably as an effect of stirring.15
Figure 13. Transition electron micrographs of RuNPs after CYD hydrogenation for Ru0 (left), Ru25 (middle) and
Ru50 (right)
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The apparent resistance to coalescence of the NPs means that they may be tested for their
recyclability. Subsequently, using the most selective catalyst, Ru0, recycling experiments were
performed, by extracting in vacuo and quantifying the volatiles after each 90 minute run. More
CYD was then added for hydrogenation. From the results (Table 8 and Figure 14) it can be seen
that the activity and selectivity both remain high after 5 recycles, diminishing only slightly with
each run. This small decrease of course is attributable to the gradual coalescence of the NPs,
leading to a diminution in the number of active surface sites and larger, less selective NPs.
Indeed, TEM images obtained of the NPs after all recycling experiments showed that the NPs
had undergone coalescence to attain an average diameter of 1.8 ± 0.5 nm, approaching the size of
Ru25, and of course exhibiting a similar selectivity.
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Table 8. Results from recycling experiments in the hydrogenation of CYD using Ru0 and comparison with results
obtained for Ru25 and Ru50
Pressure H2 / Conversion at 90 Selectivity Size after
TON TOF / h-1
bar min CYE catalysis / nm
Ru0 (1.1 nm) 1.2 66 % 97 % 70 46 1.3 ± 0.4
Ru0 recycle 1 1.2 73 % 95 % 76 51 -
Ru0 recycle 2 1.2 69 % 94 % 73 49 -
Ru0 recycle 3 1.2 68 % 89 % 71 47 -
Ru0 recycle 4 1.2 64 % 86 % 67 45 -
Ru0 recycle 5 1.2 65 % 86 % 68 45 1.8 0.5
Ru25 (2.3 nm) 1.2 75 % 86 % 79 53 2.1 ± 0.5
Ru50 (2.9 nm) 1.2 83 % 80 % 87 58 2.7 ± 0.5
179
55 100
TOF
Selectivity for cyclohexene
50
Selectivity for cyclohexene / %

90
45
80
-1
TOF / h
40
70
35
60
30
tel-00708600, version 1 - 15 Jun 2012
25 50
1 2 3 4 5 6
Cycle
Figure 14. Evolution of TOF and selectivity with catalyst recycling
4.9 Conclusion
In this chapter, the catalytic hydrogenation in [C1C4Im][NTf2] of 1,3-cyclohexadiene

(CYD), cyclohexene (CYE), limonene (Lim) and styrene (Sty) have been used as probes for the
relationship between size and catalytic performance of RuNPs.
Firstly, tailor-made, size-controlled and zero-valent RuNPs (1 to 3 nm) were generated
from the decomposition of [Ru(COD)(COT)] under H2 in [C1C4Im][NTf2], by varying the
experimental conditions. RuNPs were fully characterised in situ by TEM and HREM to
determine their sizes and demonstrate their degree of crystallinity, and ex situ by XPS to verify
their zero oxidation state.
Secondly, all catalytic reaction compositions were carefully calculated in order that all
parameters except particle size were maintained constant, i.e. Rus concentration, substrate/Rus
ratio and substrate/IL ratio, the latter governing solvation phenomena and mass transfer factors
(viscosity and diffusivity).
180
For the hydrogenation of Lim, as for Sty, the effect of NP size on activity is not
significant. However, the selectivity is NP size-dependent at 30 °C, 100 % selectivity for p-1-
menthene being observed at low conversion ( 20 %) for the smallest NPs – Ru0.
Conversely, it was found that for catalytic hydrogenation of CYD, the activity of catalyst
increases with the NP size in agreement with the literature results on heterogeneous catalysts.
Contrarily to activity, in the hydrogenation of CYD, the selectivity for CYE versus CYA drops
from 97 % to 80 % when the RuNP size increases from 1.1 to 2.9 nm.
Both results, activity and selectivity, are in agreement with a mechanism involving a π-
bond activation and a double coordination of diene substrates, necessitating several neighbouring
surface atoms only found in facial positions on the larger NPs. Furthermore, these RuNPs show a
high level of recyclability with neither loss of activity nor significant agglomeration.
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4.10 Outlooks
A commonly reported advantage to generating NPs in ILs is that the resulting surfaces
are ligand free, and therefore the potential in catalysis is maximised. However, certain ligands
may have an important electronic effect on the catalyst. In our laboratory, we have recently
reported a synthesis of RuNPs involving amine ligands in ionic liquids, giving very small NPs
(1.2 nm) with a narrow size distribution, active in aromatic hydrogenation at 75 °C without
coalescence.38 It is planned therefore to compare the catalytic performance, i.e. activity,
selectivity and recyclability of ligated and ligand-free NPs.
The partial hydrogenation of aromatics is a challenging issue. The complicated Asahi
process, involving a tetraphasic mixture incorporating colloidal ruthenium as the catalyst, is the
only industrial process, and can convert benzene to CYE with a yield of 60%.39 In this work and
in similar systems,25 the partial hydrogenation of aromatics has been reported, using the
solvation properties of ILs to extract partially hydrogenated species. Future work is planned to
firstly determine whether these species are a result of partial hydrogenation or dehydrogenation
of fully hydrogenated species, and then attempt to optimise conditions, for instance using wet
ILs, to selectively extract the desired product in higher yields.
181
4.11 Experimental section
4.11.1 Materials and methods

1,3-cyclohexadiene, styrene and limonene (99% Aldrich) were distilled prior to use. To
produce commercially unavailable menthane for characterisation, a 5 mL sample is stirred with 1
mL of Ru50, and heated to 75°C under 4 bars of H2 during 72h to force complete hydrogenation.
Analysis of the products obtained by GC-MS show that no limonene remains. The majority
products are the two diastereoisomers of p-menthane, and p-1-menthene, but also small amounts
of previously unobserved menthene isomers, cis- and trans-p-2-menthene and p-3-menthene, e,
f, and g in Scheme 5. This indicates the possibility of alkene isomerisation using RuNPs.
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Scheme 5. Side products in the hydrogenation of limonene.

4.11.2 Catalysts synthesis
RuNPs were synthesised as already reported, here varying the temperature of
decomposition of [Ru(COD)(COT)]; Ru0 at 0 °C, Ru25 at 25 °C, Ru50 at 50 °C and Ru75 at
75 °C.15
4.11.3 Determination of particle size by TEM
Transmission electron microscopy (TEM) experiments were performed directly in the IL
media. A thin film of RuNP solution in IL was deposited on a carbon film supported by a copper
grid. Conventional TEM micrographs were obtained at the Centre Technologique des
Microstructures, Université Claude Bernard Lyon 1, Villeurbanne, France, using a Philips 120
CX electron microscope with acceleration voltage of 120 kV. Size distribution histograms were
constructed from the measurement of at least 200 different nanoparticles assuming a near
spherical shape and random orientation. High resolution electron micrographs were obtained at
182
the “TEMSCAN” centre of the Université Paul Sabatier Toulouse 3, Toulouse, France, using a
JEOL JEM 200CX electron microscope with acceleration voltage of 200 kV.
4.11.4 X-ray Photoelectron Spectroscopy (XPS)
X-ray photoelectron spectroscopy was performed in a Kratos Axis Ultra DLD
spectrometer, using a monochromatic AlKα X-ray with a pass energy of 20 eV and a coaxial
charge neutraliser. The base pressure in the analysis chamber was better than 5×10−8 Pa. XPS
spectra of Ru3p, C1s, Si2p and O1s levels were measured at a normal angle with respect to the
plane of the surface. High resolution spectra were corrected for charging effects by assigning a
value of 284.6 eV to the C1s peak (adventitious carbon). Binding energies were determined with
an accuracy of ± 0.2 eV. The data were analysed using Casa-XPS (v 2.3.13) employing a Shirley
background subtraction prior to fitting and a peak shape with a combination of Gaussian and
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Lorentzian (30% Lorentzian). High resolution spectra were acquired in the region of Ru 3p as the
Ru 3d region overlaps with the C 2p region of the residual ionic liquid.
4.11.5 Catalytic tests
Catalytic solutions were made in a glove box and left stirring for 12 h in a closed system
to ensure homogenity. 0.5 mL aliquots were transferred to identical Schlenk tubes containing
cross-shaped magnetic stirrer bars. The argon atmosphere was removed and the solution
degassed in vacuo whilst cooling in liquid nitrogen (−196 °C). For reactions at 30 °C, 6 of these
Schlenk tubes were placed in a thermostatic carousel to ensure identical temperature and stirring
conditions. After 30 minutes, when the temperature had stabilised, the Schlenk tubes were
opened to 1.2 bars of H2. After t minutes, a Schlenk tube was isolated and opened to air,
releasing the H2 atmosphere thus stopping the reaction. The solution was entirely dissolved in
10 mL of acetonitrile containing a 1 molar concentration of toluene. The composition of the
mixture was determined by gas phase chromatography using toluene as the internal standard. For
reactions at 75 °C the same procedure was used as above. For reactions at -2 °C, the Schlenk
tubes were cooled independently in a cryostatic bath and stirred. After 30 minutes, when the
temperature had stabilised, the Schlenk tubes were opened to 1.2 bars of H2. After t minutes, a
Schlenk tube was isolated and opened to air, releasing the H2 atmosphere thus stopping the
reaction. The solution was entirely dissolved in 10 mL of acetonitrile containing a 1 molar
concentration of toluene. The composition of the mixture was determined by gas phase
chromatography using toluene as the internal standard.
183
4.11.6 Product quantification

The products were quantitatively analysed by gas chromatography on a HP-6890
chromatograph equipped with a flame ionisation detector (FID) and a HP-1 (crosslinked
methylsiloxane) column (L: 30 m, int: 0.32 mm, film thickness: 0.25 µm). The injector and
detector temperature was 270 °C, and the injection volume was 1 µL. The programme was as
follows: initial temperature 70 °C for 13.5 minutes; ramp 40 °C/min to 250 °C, hold 2 minutes.
4.11.7 GC-MS
The gas chromatograph was a Focus DSQ from ThermoElectron. Xcalibur software was
used for data acquisition and data treatment. The injector temperature was set at 220 °C, the
transfer line at 280 °C and the ion source at 200 °C. The analysis was made on a fused-silica
capillary column (J&W Scientific), 30 m x 0.25 mm i.d., with DB5-MS stationary phase and a
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0.25 μm film thickness. The carrier flow (He) was maintained at 1.2 mL min-1. The column
temperature programme was as follows: initial temperature 70°C, maintained for 2 min, then
ramped at 15 °C min-1 to 310 °C, which was maintained for 10 min.
4.11.8 Density and viscosity
The mixtures of and CYD at different compositions were prepared gravimetrically
following the procedure already described.[27] The viscosity of the mixture was measured at
298.15 K (controlled to within ± 0.005 K and measured with the accuracy better than ± 0.05 K)
using a rolling ball viscometer from Anton Paar, model AMVn.[27] The overall uncertainty of
the viscosity is estimated as ± 2.0 %. The densities of the mixtures, necessary to calculate the
viscosities were measured in an Anton Paar vibrating tube densimeter model 512 P, at 298.15 K
(measured by a calibrated PRT with an accuracy of ± 0.02 K). The overall uncertainty of the
density is estimated as ± 0.01 %.
4.11.9 Solubility
To measure the solubility, 1 mL of the substrate was stirred with the ionic liquid in a
closed system at 298.15 K for 12 h then left to settle for a further 2 h. A 0.1 mL sample of the
ionic liquid phase was weighed and its composition determined by GC using the procedure
described in section 4.11.6. Tests were repeated 4 times for each substrate, to guarantee
reproducibilty.
184
4.12 References
1. M. Valden, X. Lai and D. W. Goodman, Science, 1998, 281, 1647.

2. A. T. Bell, Science, 2003, 299, 1688 –1691.
4. K. Lee, M. Kim and H. Kim, J. Mater. Chem., 2010, 20, 3791-3798.
5. A. Z. Moshfegh, J. Phys. D: Apply. Phys., 2009, 42, 233001(233032pp.).
6. G. A. Somorjai and J. Y. Park, Top Catal., 2008, 49, 126-135.
7. H. Boennemann, K. S. Nagabhushana and in Metal Nanoclusters in Catalysis and
Materials Science: The Issue of Size Control eds. B. Corain, Schmid, G., Toshima, N.,
Elsevier B.V, Amsterdam, 2008, pp. 21-48.
tel-00708600, version 1 - 15 Jun 2012
8. H. Bönnemann, K. S. Nagabhushana and R. M. Richards, in Nanoparticles and Catalysis,

ed. D. Astruc, Wiley-VCH, Weinheim, 2008.
9. H. Tada, T. Kiyonaga and S. Naya, Chem. Soc. Rev., 2009, 38, 1849.
10. N. D. Spencer, Schoonmaker R. C and G. A. Somorjai, J. Catal., 1982, 74, 129-135.
11. M. Ojeda, S. Rojas, M. Boutonnet, F. J. Perez-Alonso, F. J. Garcia-Garcia and J. L. G.
Fierro, Appl. Catal., A 2004, 274, 33-41.
12. H. Song, R. M. Rioux, J. D. Hoefelmeyer, R. Komor , K. Niesz, M. Grass, P. D. Yang
and G. A. Somorjai, J. Am. Chem. Soc. 2006, 128, 3027-3037.
13. K. Bratlie, H. Lee, K. Komvopoulos, P. Yang and G. A. Somorjai, Nano Lett., 2007, 7,
3097–3101.
16. N. Bedford, C. Dablemont, G. Viau, P. Chupas and V. Petkov, J. Phys. Chem. C, 2007,
111, 18214-18219.
17. R. Nyholm and N. Martensson, J. Phys. Chem., 1980, 13, L279.
18. J. A. Van Bokhoven and J. T. Miller, J. Phys. Chem. C, 2007, 111, 9245.
19. V. A. Finkel, M. I. Palatnik and G. P. Kovtun, Phys. Met. Metall., 1971, 32, 231.
20. R. A. Van Santen, Acc. Chem. Res., 2009, 42, 57-66.
185
21. P. S. Campbell, A. Podgorsek, T. Gutel, C. C. Santini, A. A. H. Padua, M. F. Costa

Gomes, F. Bayard, B. Fenet and Y. Chauvin, J. Phys. Chem. B, 2010, 114, 8156-8165.
22. J. Huang, T. Jiang, B. Han, H. Gao, Y. Chang, G. Zhao and W. Wu, Chem. Commun.,
2003, 1654-1655.
23. Y. Chauvin, S. Einloft and B. H. Olivier, Ind. Eng. Chem. Res., 1995, 34, 1149-1155.
24. A. P. Umpierre, G. Machado, G. H. Fecher, J. Morais and J. Dupont, Adv. Synth. Catal.,
2005, 347, 1404-1412.
3740.
26. T. Umecky, Y. Saito and H. Matsumoto, J. Phys. Chem. B, 2009, 113, 8466-8468.
tel-00708600, version 1 - 15 Jun 2012
27. T. Umecky, Y. Saito and H. Matsumoto, Electrochem. Soc. Trans., 2010, 25, 23-29.
28. M. A. Vorotyntsev, V. A. Zinovyeva and M. Picquet, Electrochim. Acta 2010, 55, 5063-
5070.
29. D. Y. Murzin, Chem. Eng. Sci., 2009, 64, 1046-1052.
30. A. Binder, M. Seipenbusch, M. Muhler and G. Kasper, J. Catal., 2009, 268, 150-155.
31. N. Semagina, A. Renken and L. Kiwi-Minsker, J. Phys. Chem. C, 2007, 111, 13933-
13937.
Padua and Y. Chauvin, Phys. Chem. Chem. Phys., 2010, 12, 4217-4223.
33. M. Saeys, M.-F. Reyniers, M. Neurock and G. B. Marin, Surf. Sci., 2006, 600, 3121-
3134.
34. W. L. Manner, G. S. Girolami and R. G. Nuzzo, J. Phys. Chem. B, 1998, 102, 10295-
10306.
35. J. Silvestre-Albero, G. Rupprechter and H.-J. Freund, J. Catal., 2006, 240, 58-65.
36. E. Bogel-Lukasik, I. Fonseca, R. Bogel-Lukasik, Y. A. Tarasenko, M. Nunes da Ponte,
A. Paiva and G. Brunner, Green Chem., 2007, 9, 427-430.
37. A. Ahosseini and A. M. Scurto, Int. J. Thermophys. , 2008, 29, 1222-1243.
38. G. Salas, Santini C. C., K. Philippot, V. Collière, B. Chaudret and B. Fenet, Dalton
Trans., submitted 2010.
39. H. Nagara, Appl. Surf. Sci., 1997, 121/122, 448-451.
186
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General Conclusion
187
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188
General Conclusion
General Conclusion
This thesis focuses on the peculiar physical-chemical properties of imidazolium based ionic
liquids – more precisely, how we may exploit these properties in catalysis and how they may
influence the outcome of the catalytic process. In this respect, the following two important
factors were predominantly investigated:
1. The specific solvation properties of ionic liquids (ILs) – How may these be utilised to
generate and stabilise in situ catalytically active metal nanoparticles (NPs) of
controlled size?
2. The distinctive thermophysical properties of ILs (viscosity and diffusivity) – What is
the influence on catalytic activity in both homogeneous and NP catalysis performed
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in situ?
First of all, a review of the most significant literature results in the synthesis and catalytic
applications of ruthenium nanoparticles (RuNPs) highlighted the dependence of the catalytic
properties on their size and surface properties. The ability to predict and control the size of the
NPs produced, is therefore of the utmost importance. Furthermore, producing NPs free of ligands
and other surface contaminants can only be advantageous in catalysis. Decomposition of
organometallics under H2 presents the advantage of producing only inert alkane by-products,
easily removed under vacuum, while the use of ILs produces stable NPs of controlled size
without the need for stabilising additives. Marrying these two techniques leads to a route to
stable NPs of controlled size, with maximum surface availability. Consequently, throughout this
work, NPs are produced by the decomposition of organometallic complexes under H2 in ILs.
It has previously been explained that the phenomenon of crystal growth of RuNPs,
generated in situ in imidazolium-based ILs from Ru(COD)(COT), is controlled by the size of
non-polar domains created by the grouping of lipophilic alkyl chains and segregated by a rigid 3-
D network of ionic channels. However, no information was available to explain the remarkable
stability of the resulting systems. Is the RuNP surface really contaminant-free?
In this work, we have brought to light firstly the close proximity of the RuNPs to the non-
polar R group of the cation, through in situ labelling experiments (deuteration and reduction),
thus corroborating the hypothesis that the RuNPs are located within these non-polar pockets.
Addition of water, destroying the ionic network, induces agglomeration of the RuNPs,
189
General Conclusion
supporting the fact that the RuNPs are originally isolated within non-polar pockets by the 3-D
network of ionic channels. Secondly, the presence of surface hydrides and their role in the
stabilisation of the nanoparticles is demonstrated. The stabilisation mechanism is thus analogous
to that described in colloidal organic solutions.
A
HO N
OH N
Me Me methanol A
N
R N
H
A
R
H N
R
H
N
H
Me Me OH THF
N N
H R A
N
R H A
HO A
N
N
A
H by analogy N
N
RH R
H
N
H N
N
R H H
H H N
A A
R
A A
N N
R N
N
N RH R A
N
N N N
H H
R
H A
R H
cyclooctane H A
H H N R N
N
A
N
Literary results give conflicting views on the mechanism for the growth and stabilisation
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of transition metal nanoparticles in ionic liquids, leading to the conclusion that this depends on
the nature of the metal, its precursor complex, the synthetic route and/or the ionic liquid used.
This led to the question of whether the same would be true of NPs generated in the same way
from an analogous organometallic compound of another metal. For this reason, we have also
investigated the possibility of generalising these findings to the generation of nickel
nanoparticles, NiNPs, as the organometallic complex bis(1,5-cyclooctadiene)nickel, Ni(COD)2,
analogous to Ru(COD)(COT), is commercially available.
The synthesis of NiNPs from Ni(COD)2 under H2 (4 bar) was carried out in various
imidazolium based ionic liquids at 0 °C and 25 °C. Imidazolium cations substituted with longer
chains [C1C6Im][NTf2], [C1C8Im][NTf2] and [C1C10Im][NTf2], were found to offer fairly good
media for the preparation and stabilisation of nickel nanoparticles. NiNP size increased with
increasing chain-length and in this way we were able to control NiNP size. Additionally, upon
decreasing the reaction temperature to 0 °C, we were able to produce smaller NiNPs than those
produced in the same IL media at 25 °C. The presence of surface hydrides on these NiNPs, as on
RuNPs, has been evidenced by hydrogenation of ethylene in the absence of hydrogen. The
resulting NiNPs in these ILs were found to be larger than RuNPs produced in the same media.
This can be largely attributed to differences in the nucleation and growth processes for the two
metals.
Unexpectedly, spontaneous decomposition of Ni(COD)2 occurred without the addition of
hydrogen upon dissolution into imidazolium ILs with short alkyl chains; [C1C2Im][NTf2],
190
General Conclusion
[C1C4Im][NTf2] and [C1C1C4Im][NTf2]. In [C1C2Im][NTf2] and [C1C4Im][NTf2], TEM

micrographs showed NiNPs of fairly large diameter were formed, as well as sponge-like super
agglomerates. In [C1C1C4Im][NTf2] well dispersed NiNPs are formed. In these cases, an
explanation concerning the activation of the acidic protons on the imidazolium ring and the
consequent nitrogen heterocyclic carbene formation leading to rapid decomposition of the
complex, has been proposed. This is the first case of the use of pure, non-functionalised ILs for
the direct decomposition of organometallics.
Bu + Bu 1,3-COD
+ 2 (1,5-COD)
N N
N
A- N
Bu Me
C2
A- + Ni(1,5-COD)2 C2 [Ni] H N
H
Me
N
H 1,5-COD
Me
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C2H4
?
Bu N + N N + N
Bu Me Bu Me
N C2 C2
+ H A -
A-
C Et Bu
N 2 H
Me = Ni
On changing the anion of the IL to the more strongly co-ordinating tetrafluoroborate

[C1C4Im][BF4], the acidic protons of the imidazolium ring were protected, and more controlled
NiNP formation took place, only in the presence of hydrogen. This medium was therefore
successfully used to synthesise NiNPs smaller than 4 nm in diameter, (smaller than previously
reported in the literature by chemical methods!)
We have also demonstrated that small monodisperse and zero-valent tantalum
nanoparticles, Ta(0)NPs, may be generated under mild conditions, by the decomposition of the
organometallic complex tris(neopentyl)neopentylidene-tantalum(V), under H2 in imidazolium-
derived ionic liquids. The control of the size and the factors of stabilisation of these NPs in ionic
liquids are currently under investigation. This method has opened up the possibility of facile
access to other oxophilic metal nanoparticles, which can only be achieved in ILs.
If we are to perform catalysis in situ we must understand the role that the ILs may play.
Therefore, we have attempted to determine the physical-chemical parameters influencing a
model homogeneous reaction, namely the hydrogenation of 1,3-cyclohexadiene (CYD) using an
Osborn-type catalyst [Rh(COD)(PPh3)2]NTf2 in different ionic liquids; 1-butyl-3-
191
General Conclusion
methylimidazolium bis(trifluoromethylsulfonyl)imide, [C1C4Im][NTf2] and 1-butyl-2,3-

dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [C1C1C4Im][NTf2].
Firstly, the solvation of CYD in the two ILs was investigated by molecular dynamics
simulations and ROESY NMR experiments. In both ILs, CYD is found to be located in the
lipophilic domains. In [C1C1C4][NTf2], CYD is found closer to the C2-Me, whereas in
[C1C4Im][NTf2], strong interactions between C2-H and the anion [NTf2] do not allow for such
proximity.
Secondly, the role of mass transport factors has been studied in both ILs. For this, the
viscosity, η, of CYD-IL mixtures of various molar ratios, R = CYD/IL, was measured, and
shown to vary radically with R. The viscosity values measured in [C1C1C4Im][NTf2] were
consistently found to be roughly double those measured in [C1C4Im][NTf2].
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The chosen model catalytic reaction was the hydrogenation of 1,3-cyclohexadiene

(CYD), which occurs in two steps: (1) the ligand exchange [Rh(COD)(PPh3)2]NTf2 to
[Rh(CYD)(PPh3)2]NTf2 (COD=1,5-cyclooctadiene), and (2) the catalytic hydrogenation of CYD
itself. It was found that both steps, monitored here by UV-vis spectroscopy, are twice as fast in
[C1C4Im][NTf2], implying that the reaction rate is strongly dependent on the viscosity and
diffusion of the substrate. In conclusion, when comparing catalytic activity in ILs, the differences
in physical-chemical properties must be taken into account, in particular the mass transport
factors, which play a decisive role.
(1) (2)
(1) (2)
IL1
IL1
IL2
IL2
rate α η-1
192
General Conclusion
Finally, the catalytic hydrogenation of 1,3-cyclohexadiene (CYD), cyclohexene (CYE),

limonene (Lim), and styrene (Sty) has been used as a probe for the relationship between size and
catalytic performance of RuNPs in [C1C4Im][NTf2].
Firstly, tailor-made, size-controlled and zero-valent RuNPs (1 to 3 nm) were generated
from the decomposition of [Ru(COD)(COT)] under H2 in [C1C4Im][NTf2], by varying the
experimental conditions. RuNPs were fully characterised, both in situ by transition electron
microscopy (TEM) and high resolution electron microscopy (HREM), to determine their sizes
and demonstrate their degree of crystallinity, and ex situ by X-ray photoelectron spectroscopy
(XPS), to verify their zero oxidation state. Secondly, all catalytic reaction compositions were
carefully calculated in order that all parameters except particle size were maintained constant, i.e.
Rus concentration, substrate/Rus and substrate/IL ratios, the latter governing solvation
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phenomena and mass transfer factors (viscosity and diffusivity).

For the hydrogenation of Lim, as for Sty the effect of NP size on activity is not
significant. However, the selectivity is NP size-dependent at 30 °C – 100 % selectivity for p-1-
menthene observed at low conversion ( 20 %) for the smallest NPs.
Nevertheless, it was found that for catalytic hydrogenation of CYD, the activity of the
catalyst increases with the NP size in agreement with literature results on heterogeneous
catalysts. Contrarily to activity, in the hydrogenation of CYD, the selectivity for CYE versus
CYA drops from 97 % to 80 % when the RuNP size increases from 1.1 to 2.9 nm.
Both results, activity and selectivity, are in agreement with a preferred mechanism
involving a π-bond activation and a double coordination of diene substrates, necessitating several
neighbouring surface atoms only found in facial positions on the larger NPs.
In summary, ILs have been shown to be excellent media for the controlled growth and
stabilisation of metal NPs, and the importance of the size control in catalysis has been proven.
193
General Conclusion
Outlooks
During this work, the synthesis and stabilisation of size-controlled RuNPs in imidazolium
ionic liquids has been well established and understood. Their use in catalysis has been touched
upon using some model reactions, during which, the partial hydrogenation of styrene giving
ethylcyclohexene was observed. Although the yield was poor, this is nonetheless an interesting
result, as the partial hydrogenation of aromatic cycles to cyclic olefins is an important and
challenging industrial process. By investigating further this reaction, in order to understand the
mechanism, it may be possible to optimise conditions in order to increase the yield of this
interesting product. Is this product a result of partial hydrogenation, or full hydrogenation
followed by dehydrogenation? Can we extract this product by using additive containing ILs (e.g.
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H2O to alter the thermophysical properties and the solubility or organic moieties)?
It may also be interesting to use these well defined catalytic systems to attempt more
interesting catalytic reactions, such as alkane oxidations or nitrogen activation.
Finally, some important and interesting preliminary results have been obtained regarding
the possiblility of producing zero-valent NPs of oxophilic metals, such as tantalum. This opens
up new innovative pathways to produce nano-objects with reduced process cost and could be of
great potential interest in the drive for smaller and more efficient electronic devices. This is
currently under development in collaboration with the “Commissariat à l’Énergie Atomique
(CEA)”, and is the subject of two Ph.D. theses.
194
i
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Appendix 1
Characterisation of Nickel
Nanoparticles by XPS
195
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196
Appendix 1 Characterisation of Nickel Nanoparticles by XPS
Characterisation of Nickel Nanoparticles by

X-ray Photoelectron Spectroscopy
As spontaneous or H2 induced decomposition of Ni(COD)2 could take place in
[C1C6Im][NTf2] depending on the temperature, comparisons of the resulting particles could be
made without changing the solvent.
X-ray photoelectron spectroscopy can be used to determine elemental composition and
oxidation states in a sample. Due to the weak concentration of the solution and the fact that only
photoelectrons from a maximum depth of 10 nm may be observed, no peaks corresponding to Ni
binding energies were observed when the analyses were carried out directly on the NiNP/IL
solutions. Samples were therefore prepared by filtering the NiNPs onto silica under inert
tel-00708600, version 1 - 15 Jun 2012
atmosphere and eliminating as much IL as possible. The XPS spectrum in the Ni 2p region for
NPs prepared by decomposition under H2 is shown in Figure 1. It is clear that two species exist,
Ni0 and NiII.
Figure 1. Ni 2p region of XPS spectrum obtained for NiNPs in [C1C6Im][NTf2]
The data gathered during XPS analyses are tabulated in Table X. It can be seen that in
both cases a large peak is present corresponding to NiII. It should be noted that when transferring
the sample into the sample treatment chamber, it was subjected to air and ambient conditions for
a short period of time (< 5 minutes). The high level of oxidation may be a result of air exposure.
For this reason we rerun the analyses of the samples after a longer exposure period in air
197
Appendix 1 Characterisation of Nickel Nanoparticles by XPS
(~ 5 hours). In the case of NiNPs produced through the H2 decomposition of Ni(COD)2, the
intensity of the Ni 2p bands corresponding to NiII was greatly increased after prolonged air
exposure, where as for the NiNPs produced from spontaneous decomposition, the amount of Ni II
remained constant. This could be explained by two factors; 1) the NiNPs produced by
spontaneous decomposition exhibit less Ni surface susceptible to oxidation; 2) these NiNPs were
already oxidised at the surface by oxidative addition of the imidazolium ring producing carbene
ligands.
Table 1. XPS data gathered for NiNPs produced by autodecomposition and H 2 decomposition of Ni(COD)2 in the
IL [C1C6Im][NTf2]
Sample Ni 2p peak 2p 3/2 2p 1/2 Doublet Area Ratio
separation
Ni(0):NiII
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(1) Ni(0) 853.7 873.4 19.7 1134 0.32

Decomposition under
4 bars H2 at 25 °C in NiII 861.1 880.8 19.7 3515
[C1C6Im][NTf2]
(2) Ni(0) 853.7 873.1 19.4 717 0.15
(1) After exposure to air
(5 h) NiII 860.8 880.6 19.8 4754
(0)
(3) Ni 853.9 872.9 19 2265 0.29
Decomposition on
stirring at 40 °C NiII 861.3 881.1 19.8 7703
in[C1C6Im][NTf2]
(4) Ni(0 853.2 872.8 19.6 3163 0.27
(3) After exposure to air
(5 h) NiII 861.3 881.4 20.1 11709
The results obtained are inconclusive, as we cannot be sure whether the oxidised nickel
was due to air exposure or if it already existed in the NiNP/IL mixture. Future tests are planned
to run XPS using a system for transferring the sample into the chamber without exposure to air.
Magnetic measurements using a sensitive SQUID (Superconducting Quantum
Interference Device) may also be useful in characterising the nickel nanoparticles. FC-ZFC (field
cooled – zero field cooled) measurements of the magnetisation can be used to find the blocking
temperature (Tb) of the superparamagnetic NPs, which may be related to their size. The
percentage of non-oxidised Ni0 may also be estimated from the magnetic hysteresis curve at
obtained at low temperature (generally 2 K). This work is currently in progress.
198
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Publications
ii
Appendix 2
199
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200
Appendix 2 Publications
Publications
The work reported in this thesis has contributed to the following papers and patents. Copies of
the papers can be found in this appendix.
Papers
1) “A novel stabilisation model for ruthenium nanoparticles in imidazolium ionic liquids: in situ
spectroscopic and labelling evidence.”
P. S. Campbell, C. C. Santini, D. Bouchu, B. Fenet, K. Philippot, B. Chaudret, A. A. H. Padua

and Y. Chauvin, Phys. Chem. Chem. Phys., 2010, 12, 4217-4223.
tel-00708600, version 1 - 15 Jun 2012
2) “How do Physical-Chemical Parameters Influence the Catalytic Hydrogenation of 1,3-

Cyclohexadiene in Ionic Liquids?”
P. S. Campbell, A. Podgoršek, T. Gutel, C. C. Santini, A. A. H. Pádua, M. F. Costa Gomes, F.

Bayard, B. Fenet and Y. Chauvin, J. Phys. Chem. B., 2010, 114, 8156-8165.
3) “Olefin hydrogenation by ruthenium nanoparticles in ionic liquid media: Does size matter?”
P. S. Campbell, C. C. Santini, F. Bayard, Y. Chauvin, V. Collière, A. Podgorsek, M.F. Costa

Gomes and J. Sá., J. Catal., 2010, 275, 99-107.
4) “Imidazolium ionic liquids as promoters and stabilising agents for the preparation of metal(0)
nanoparticles by reduction and decomposition of organometallic complexes.”
M. H. G. Prechtl, P. S. Campbell, J. D. Scholten, G. B. Fraser, G. Machado, C. C. Santini, J.

Dupont and Y. Chauvin, Nanoscale, 2010, doi: 10.1039/C0NR00574F
Patents
1) “Mémoires et Interconnections à base de Nanotubes de Carbone.” Catherine Scampucci (ep.
Santini), Jean-Marie Basset, Thibaut Gutel, Paul Campbell, Simon Deleonibus, Paul Haumesser,
Brevet CEA-LETI /Univ Lyon 1 CNRS/LCOMS : Fr 0901464 27/03/09
2) “Procédé de réalisation d’un dispositif mémoire à grille flottante.” Catherine Scampucci (ep.
Santini) , Jean-Marie Basset, Thibaut Gutel, Paul Campbell, Simon Deleonibus, Paul Haumesser,
Brevet CEA-LETI /Univ Lyon 1 CNRS/LCOMS : Fr 0901463 27/03/09
201
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202
Appendix 2
Publications
PAPER www.rsc.org/pccp | Physical Chemistry Chemical Physics
A novel stabilisation model for ruthenium nanoparticles in imidazolium

ionic liquids: in situ spectroscopic and labelling evidencew
Paul S. Campbell,a Catherine C. Santini,*a Denis Bouchu,b Bernard Fenet,c
Karine Philippot,d Bruno Chaudret,d Agı́lio A. H. Páduae and Yves Chauvina
Received 1st December 2009, Accepted 8th February 2010
First published as an Advance Article on the web 10th March 2010
DOI: 10.1039/b925329g
In situ labelling and spectroscopic experiments are used to explain the key points in the stabilisation
of ruthenium nanoparticles (RuNPs) generated in imidazolium-based ionic liquids (ILs) by
decomposition of (Z4-1,5-cyclooctadiene)(Z6-1,3,5-cyclooctatriene)ruthenium(0), Ru(COD)(COT),
under dihydrogen. These are found to be: (1) the presence of hydrides at the RuNP surface and, (2)
the confinement of RuNPs in the non-polar domains of the structured IL, induced by the rigid 3-D
organisation. These results lead to a novel stabilisation model for NPs in ionic liquids.
Introduction anions, such as [BF4]ÿ, [PF6]ÿ, or [N(SO2CF3)2]ÿ,7,8 all

without compelling evidence.3 Other possible explanations
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Metal nanoparticles (MNPs) have lately become a new and include ligand-type stabilisation by the IL moieties. Indeed,
exciting area of research interest. Defined as particles, whose this has been illustrated for IrNPs in an imidazolium based IL,
dimensions are on the nanoscale, they coincide with a transition where H/D labelling experiments provided evidence for
between bulk and molecular states, and exhibit unique charac- the formation of N-heterocyclic carbenes on the surface of
teristics related to the discontinuities and quantum effects of the NPs.8,9
such a transition, e.g. enhanced magnetic and catalytic proper- Very recently, a relationship between the size of IL
ties, etc. The controlled synthesis of nanoparticles in the range non-polar domains calculated by molecular dynamics simu-
of 1–10 nm is still an ongoing challenge, as is the under- lation and the mean diameter of ruthenium nanoparticles
standing of their stabilisation and agglomeration.1–4 Indeed, (RuNP), (generated in situ from the organometallic complex
transition-metal nanoparticles remain only kinetically stable, (Z4-1,5-cyclooctadiene)(Z6-1,3,5-cyclooctatriene) ruthenium(0),
the thermodynamic minimum being bulk metal. Consequently, Ru(COD)(COT), has been found.10 This suggests that the
substantial effort has been centred on stabilising transition- phenomenon of crystal growth occurs in these non-polar
metal nanoparticles. Furthermore, their formation and stabilisation domains of the ILs and is controlled by the local concentration
(inhibition of coalescence) are closely related issues.3 of the precursor complex. This can be supported by the fact
In ionic liquids (ILs), particularly those based on the that imidazolium-based ILs exhibit an extended hydrogen-
imidazolium cation, NPs can be generated by several physical bond network in the liquid state and a continuous three
and chemical routes.5 Unlike traditional solvents, IL media dimensional network of ionic channels, coexisting with non-
are able to stabilise nanoparticles in the absence of further polar domains created by the grouping of lipophilic alkyl
additives such as ligands, inhibiting metal agglomeration to chains.11–13 We can thus hypothesise that the RuNPs are
the bulk.6 However, the question of precisely how ILs stabilise surrounded by these non-polar pockets.
transition metal NPs remains under debate. Likewise, some of us have reported ‘‘solvent-only’’ stabi-
Many papers have claimed possible electrostatic stabilisation lised nanoclusters prepared from the anion-free precursor
by interactions between nanoparticles and weakly coordinating Ru(COD)(COT) in THF–MeOH.14 In this work, ‘‘nano-
reactors’’ or ‘‘pockets’’ are hypothesised to be formed with
a
Universite´ de Lyon, Institut de Chimie de Lyon, cyclooctane (the by-product of the decomposition) in which
UMR 5265 CNRS-Universite´ de Lyon-ESCPE Lyon,
LC2P2, Equipe Chimie Organométallique de Surface, ruthenium is confined and the particles stabilised, Scheme 1a.15
ESCPE 43 Boulevard du 11 Novembre 1918, F-69616 Villeurbanne, Moreover, the same authors have proved the presence and the
France. E-mail: santini@cpe.fr; Fax: 33(0)472431795; stability of hydrogen atoms on the surface of RuNPs.16,17
Tel: 33(0)472431794 By analogy, novel stabilising factors for RuNPs in ILs are
b
Centre Commun de Spectrométrie de Masse, UCB Lyon 1-ESCPE
Lyon, 43 Boulevard du 11 Novembre 1918, F-69616 Villeurbanne, reported here, such as the presence of surface hydrides, and
France their encapsulation and segregation in the non-polar domains
c
Centre Commun de RMN, UCB Lyon 1-ESCPE Lyon, of the structured IL induced by the rigid 3-D organisation,
43 Boulevard du 11 Novembre 1918, F-69616 Villeurbanne, France
d
Laboratoire de Chimie de Coordination, UMR CNRS, 205, Scheme 1b. It is worth noting that ‘‘stabilising factors’’ are
route de Narbonne, F-31077-Toulouse cedex 04, France often claimed based on ex situ methods such as TEM images
e
Laboratoire de Thermodynamique des Solutions et des Polymères, and XPS experiments performed on isolated samples. In
Universite´ Blaise Pascal, Clermont-Ferrand, 24 av. des Landais, contrast, in this work, only in situ labelling methods and
63177 Aubie`re, France
w Electronic supplementary information (ESI) available: Mass spectra spectroscopic measurements made directly in the reaction
and calculations. See DOI: 10.1039/b925329g/ mixture are used to identify these stabilising factors.
This journal is
c the Owner Societies 2010 Phys. Chem. Chem. Phys., 2010, 12, 4217–4223 | 4217
Scheme 3 IL1: C4C1Im NTf2, carbon numbering of the cation.
spectrum obtained exhibits a broad peak, (w12 = 1200 Hz)

corresponding to H2, superimposed with a finer peak (w12 200 Hz)
corresponding to HD, the intensity of which increases with
Scheme 1 Stabilisation model for RuNPs in (a) organic solvent
reaction time, then remains constant, Fig. 1a. This is in
and (b) IL.
agreement with previous findings16 and allows us to assign
the HD desorption as resulting from the deuterium activation
Results and discussion on RuNPs and recombination with bound H atoms, as
The decomposition of (Z4-1,5-cyclooctadiene)(Z6-1,3,5-cyclo- observed on metal surfaces.16,23
octatriene)ruthenium(0), Ru(COD)(COT), by hydrogen is a The fact that there is B60% of H/D exchange on positions
well known route to obtaining RuNPs, in both organic18,19 2, 4 and 5 of the imidazolium ring, as proved by 1H and
2
and ionic liquid media.5,20 The main advantage of this halogen- H NMR spectra of the IL, Fig. 1b, could suggest that the HD
free synthesis is that the only side product, cyclooctane, is easily formed is due to this exchange and not from putative surface
removed under vacuum, Scheme 2. hydrides. Note that no H/D exchange is observed when IL is
When carried out at low temperatures (0 1C) in the absence treated under D2 in the absence of RuNPs, and hence, this
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of stirring in 1-butyl-3-methylimidazolium bis(trifluorosulfonyl)- H/D exchange must involve RuNPs’ surface. To prove, there-
imide, [C1C4Im][NTf2], Scheme 3, this method yields very small fore, the presence of these surface hydrides, further experi-
NPs with a narrow size distribution (mean size: 1.1 0.2 nm ments are performed characteristic of metal surface reactivity,
calculated from TEM images captured in the ILs).21 These such as hydrogenation.
conditions are replicated throughout this work, obtaining
fresh IL-stabilised colloidal solutions, on which NMR and
mass spectroscopy experiments are performed, to determine
the key points in their stabilisation. Note that no deposition of
the RuNP suspension is observed after several months under
argon atmosphere.
In situ evidence of surface hydrides

The presence of surface hydrides has already been reported on
RuNPs in organic solvent.16 In heterogeneous catalysis, it is
well-known that under hydrogen atmosphere, the noble metal
surface is covered by hydrides.23 In ILs, is such coverage still
possible? Given the current and general stabilisation theory
concerning NPs in ILs, (strong interaction between the NPs
and anion or cation, DLVO model),1,3 the formation of surface
hydrides could be inhibited. Surface hydrides on NPs in ILs
have never been reported or envisaged.
11 H/D exchange by gas phase 1H NMR spectroscopy

Due to the low solubility of H2 in ILs,22 the remaining H2
dissolved is totally removed under high vacuum. A solution of
freshly prepared RuNPs in C1C4Im NTf2 (IL1) is, thus, first
treated under dynamic vacuum (10ÿ5 mbar, 1 or 4 h) and then
stirred under deuterium (1 bar at 25 1C, 1 or 4 d). The gas phase
is then expanded into a Young NMR tube. The 1H NMR
Fig. 1 (a) 1H NMR of gas phase (1) pure H2, (2) gas phase after 1 h
dynamic vacuum and 1 d under deuterium, (3) gas phase after 4 h
dynamic vacuum and 4 d stirring under deuterium. (b) (1) 1H NMR
spectrum of IL after NP formation under H2 and evacuation of H2 and
cyclooctane, (2)1H and (3) 2H NMR spectra of the reaction medium
after addition of D2.z
z H chemical shift of H2/HD , here 7.1 ppm, is arbitrary as no internal

Scheme 2 Generation of RuNPs in IL1. reference was used.
4218 | Phys. Chem. Chem. Phys., 2010, 12, 4217–4223 This journal is
c the Owner Societies 2010
21 Hydrogenation of ethylene It is, nevertheless, very interesting that the presence of
hydrides on ruthenium particles in ionic liquids is confirmed,
The reaction of alkenes with PVP (polyvinyl pyrrolidone)- and
since this is in agreement with the presence of these nano-
ligand-stabilised RuNPs has recently been used to quantify the
particles in uncharged lipophilic domains.
surface hydrides.17 A similar approach is transposed to a
solution of RuNPs in IL1. In the following discussion, the
RuNPs are generated in 2 mL of IL1 from 86 mmol of Stabilising effect of surface hydrides
Ru(COD)(COT). Given that the dispersion of NPs, (D, i.e.
In order to ascertain the stabilising effect of hydrogen, two
the ratio surface atoms Ns per total number of atoms Nt,
aliquots of the RuNP/IL1 solution are taken and stirred,
D = Ns/Nt), is correlated to their size,24,25 we could estimate
at 100 1C, for a period of 24 h, either under H2 or under Ar
that for RuNPs of 1.1 nm the dispersion is 75%, corresponding,
(1 bar). The resulting solutions are analysed by TEM. For the
for 86 mmol of Ru(COD)(COT), to Ns E 65 mmol of Ru
aliquot heated under H2, the mean size of the RuNPs increases
surface atoms. This IL1-stabilised RuNP solution is flushed
to 1.4 0.7 nm, and for the aliquot heated under argon, the
overnight with argon to remove dissolved hydrogen. Then, the
mean size increases to 2.2 0.8 nm. This difference in size
solution is stirred under an ethylene atmosphere (105.5 mbar)
increase with the gas atmosphere proves the inferior stability
at 25 1C. After 24 h of reaction, the system reaches equili-
of the particles when heated under argon compared to under
brium, i.e. the pressure remains constant. In the gas phase,
H2. In addition, when the RuNP/IL1 solution is treated under
analysed by GC, 11 1 mmol of ethane and 0.1 mmol of high vacuum (10ÿ6 mbar) overnight at room temperature, the
n-butane are found, corresponding to at least 22 1 mmol of TEM images show an increase in size from 1.1 0.2 nm to
surface hydride : (C2H4 + H2 - C2H6). Note that butenes 1.7 0.4 nm, Fig. 2. From these results, it appears that there is
(trans- and 1-) are also observed (0.2 mmol); however, no less coalescence of the RuNPs when heated under H2 at 100 1C
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hydrogen would be consumed in their formation. In summary, than under argon at the same temperature. This may be
IL1-stabilised RuNPs react with ethylene at room tempera- explained by the elimination of the hydrogen atoms reversibly
ture to give ethane (hydrogenation) and surface-bound alkyl bound to the metal surface, which is favoured by heating
species (homologation).26,27 under an inert atmosphere or treatment under high vacuum. In
To quantify the total amount of surface-bound alkyl conclusion, the presence of surface Ru–H stabilises the
species, the gas phase is evacuated and substituted with H2 RuNPs. These stability experiments are also consistent with
(120 mbar), and the medium is heated at 100 1C for 12 h. In the the lability of the hydrides which can be desorbed from the
gas phase, methane (4.6 mmol), ethane (8.2 mmol), propane nanoparticles in vacuo or at 100 1C.
(2.7 mmol), n-butane (1.0 mmol) and n-pentane (0.1 mmol) are
detected, corresponding to at least a further 16 mmol of
hydrides. Knowing the total amount of surface Ru atoms Evidence for close proximity between the RuNP surface and the
available (65 mmol) and the number of surface hydrides alkyl chains
consumed in all of the hydrogenation reactions (38 mmol), it The fact that in C1CnImNTf2, the non-polar domains control
is possible to calculate the ratio of hydrides per surface Ru the local concentration of Ru(COD)(COT) and consequently
atom: ca. 0.6 H per RuS, (see supplementary information for the size of RuNPs generated in situ could allow us to consider
calculationw). The combination of these results provides them as nanoreactors in which the phenomenon of crystal
substantial evidence for the existence of surface hydrides on growth occurs.10 If the RuNPs are contained within these non
the IL1-stabilised RuNPs, although the level of error in the polar pockets, it would imply that the side alkyl groups of the
quantitative results means that it is difficult to establish ILs and the RuNP surface are in close proximity or even in
accurately the quantity. The amount of H adsorbed on RuNPs interaction with one another.
is reported to be between 1.1–1.3 H/RuS for PVP- and ligand- To demonstrate this, RuNPs are synthesised under deuterium
stabilised in organic solvent,16 and between 1 and 2 H/RuS instead of hydrogen (following otherwise identical reaction
when supported on oxides.23 Note that if the IL1-stabilised conditions), since an H–D exchange on the side group of the
solutions of RuNP are treated under high vacuum (10ÿ6 mbar) IL would prove the existence of the NPs in these domains. In
overnight at room temperature instead of being flushed with the case of IL1, 2H NMR spectra show us that, as expected,
argon to remove the dissolved H2, ethylene conversion is deuteration occurs at all positions on the imidazolium ring due
negligible. to the relatively high acidity of these protons. One small peak
Indeed, hydrides bound to metal surfaces are labile and the is apparent at B1.5 ppm, which may correspond to deuteration
dissociation of H2 adsorbed on a metal surface is reversible: M + at position C8, i.e. the penultimate carbon of the butyl chain;
H2 2 MH2 2 2M–H. In the case of Ru, about 2/3 of the however, this is not irrefutable. The intensities of the peaks in
total amount of surface hydride is reversibly bound. These H the 1H NMR spectrum are reduced by roughly 30% at
species correspond to more weakly adsorbed hydrogen on the positions C2, C4 and C5, but no significant reduction in
surface, which are easily removed by evacuating the sample intensity is noted for any of the alkyl peaks. ESI mass spectra
under vacuum at 25 1C.23 Consequently, this explains why the indicate the formation of mono-, di-, tri- and a trace amount
hydrogenation (in the absence of hydrogen) of ethylene does of tetra-deuterated species. This is in agreement with the
not occur with NPs previously treated under high dynamic higher reactivity of the hydrogen bound to the imidazolium
vacuum (10ÿ5 mbar) for an extended period (12 h), because ring than to the alkyl side chain. Note that, in contrast to
very few surface hydrides remain.23,28–30 findings for IrNPs,9 where deuteration was mainly at position
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Fig. 2 TEM images captured in situ in ionic liquids and comparative size histograms of RuNPs/C1C4Im NTf2 (1.1 0.2 nm) heated to 100 1C for
24 h under H2, under Ar and kept under dynamic vacuum (10ÿ5 mbar) for 24 h at 25 1C.
C2, for RuNPs deuterium incorporation occurs equally at

positions C2, C4 and C5 on the imidazolium ring.
This experiment is then carried out in ILs with unsaturated
functional side groups: 1-(but-3-enyl)-3-methylimidazolium
bis(trifluorosulfonyl)imide (C4//C1Im NTf2), IL2 and 1-benzyl-
3-methylimidazolium bis(trifluorosulfonyl)imide (BzC1Im
NTf2), IL3. These functionalised side groups are more susceptible
to H–D exchange.
C4//C1Im NTf2, IL2. TEM images of nanoparticles synthesised

in IL2 under deuterium at 0 1C show that the nanoparticle size
distribution is similar to that of RuNPs synthesised in IL1. This
result provides supplementary evidence to suggest the size is
dictated by the length of the IL’s alkyl chain and that the RuNPs
Fig. 3 Comparative size distribution curves for RuNPs synthesised
are formed in the non-polar domains of the ILs, Fig. 3.
in IL1 and IL2, and TEM image captured in situ IL for RuNPs
For IL2, 2H NMR spectra show that deuteration takes place synthesised in IL2
at positions C8 and C9, i.e. the olefinic positions, as well as at
position C2. Surprisingly, isotopic exchange is observed
neither at positions C4 and C5 of the imidazolium ring, nor reduced to a deuterated butyl species corresponding to a TON
at positions C6 and C10. Instead, and more interestingly, a new of B16 with respect to Rus, at 0 1C, (see the supplementary
set of peaks appears at high field, corresponding to a deuterated informationw). Also, besides the peaks due to IL1 (labelled * in
butyl group due to the deuteration (reduction) of the C8QC9 Fig. 5), new peaks appear (labelled 1 in Fig. 5) in the Csp2 and
double bond, Fig. 4. Further heating of this solution under Csp3 regions, corresponding to IL2isom, in which there is an
deuterium at 50 1C for 12 h leads to a pronounced growth of isomerisation of the butenyl chain, Scheme 4.
all peaks already deuterated, but no deuteration at other
positions. The intensities of the peaks in the 1H NMR BzC1ImNTf2, IL3. The TEM images of RuNPs synthesised
spectrum of IL2 after reaction are reduced significantly at in IL3 under deuterium at 0 1C show a size distribution centred
positions C2, C8 and C9, indicating that 24% of the ionic liquid at 3.2 0.7 nm. The larger size is expected due to the higher
undergoes at least one H–D exchange, and ESI spectra (see the degree of supramolecular 3-D organisation of the ILs with the
supplementary informationw) indicate that a further 15% is side chain substituted by an aryl group.31
Fig. 6 2H NMR spectra of BzC1Im NTf2, IL3, after RuNP formation
at 0 1C under deuterium (lower) and after a further 12 h of heating to
50 1C under deuterium (upper).
and C5, but even more significantly at the aromatic positions,

where peak intensity is reduced by 35%. ESI spectra (see
supplementary informationw) indicate that 60% of the ionic
Fig. 4 (a) 1H NMR spectra of C4//C1Im NTf2, neat IL2; (b) 2H NMR
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liquid undergoes at least one H–D exchange, 50% of which is

spectra of IL2 after RuNP formation at 0 1C under deuterium; (c) 2H
NMR spectra of IL2 after RuNP formation at 50 C under deuterium;
transformed into the deuterated methylenecyclohexyl
(d) 1H NMR spectra of C4C1Im NTf2, neat. CH2C6DxH11ÿx form, with a corresponding TON of B64
with respect to Rus. Further heating of this solution under
deuterium at 50 1C for 12 h leads to a pronounced growth of
all peaks mentioned.
The hydrogenation of an aryl substituent, which does not
occur with any molecular ruthenium complexes derived from
Ru(COD)(COT), must occur on the nanoparticle surface.32
This observed reduction, therefore, clearly demonstrates the
proximity between the benzyl groups of the IL3 and the RuNP
surface.
During the formation of RuNPs under deuterium in both
IL2 and IL3, the side groups of the imidazolium rings are
saturated with deuterium. In neither case is the C2 position the
primary site for H–D exchange, in contrast to literature
results.9 Furthermore, in the case of IL2, no exchange is
observed at positions C4 and C5. Note that no exchange occurs
at positions C6 and C10 in either IL. These results indicate that
the side chains of the imidazolium are situated in close
Fig. 5 1H NMR spectra of neat IL2; IL2 after RuNP formation at proximity of the RuNP surface, where activation of the
0 1C under deuterium; neat IL1. deuterium occurs.
Role of the continuous 3-D network of ionic channels in the

isolation of RuNPs
Addition of coordinating substrates, such as water, solvate the
rigid ionic channels of the IL through the formation of strong
hydrogen bonds with the anions and also weaker hydrogen
bonds between the H bound to the C2 of the cation.33–35
Scheme 4 Isomerisation of IL2. Solvation of this ionic network alters the structure of the ionic
liquid causing aggregation of the non-polar domains.36–38 The
In the 2H NMR spectra of IL3 after reaction, deuterium following question arises: what happens to the RuNPs if the
incorporation at position C2, and at positions C4 and C5 of the structure of the IL is disrupted?
imidazolium ring and/or at the aromatic positions is observed. When, under argon atmosphere, an amount of water is
Also, a new set of aliphatic peaks appears at high field centred added to a stable RuNP suspension in IL, TEM images show
at 1.4 ppm, corresponding to a reduced methylenecyclohexyl agglomeration of the NPs after treatment, Fig. 7, supporting
group, Fig. 6. The intensities of the peaks in the 1H NMR the fact that the RuNPs are originally isolated within non-
spectrum of IL3 after reaction are reduced at positions C2, C4 polar pockets by this network. It is clear that before coalescing,
This journal is
purification. Bis(trifluoromethanesulfonyl)imide lithium salt
(Solvionic) was used without further purification.
Elemental analyses were performed at the CNRS Central
Analysis Department of Solaize.
Solution NMR spectra were recorded on Bruker Avance
300 spectrometer for 1H and 13C DRX 500 for 2H. Gas phase
1
H NMR spectra were obtained on a Bruker DRX 500
instrument at 298 K (nominal) with a resonance frequency
at 500.130 MHz.
Mass spectra were acquired on a ThermoFinnigan LCQ
Advantage ion trap instrument, detecting positive (+) an
negative (ÿ) ions in the ESI mode. Samples (1–10 mg mLÿ1
in acetonitrile) were infused directly into the source (5 mL minÿ1)
using a syringe pump. The following source parameters were
applied: spray voltage 3.0–3.5 kV, nitrogen sheath gas flow
5–20 arbitrary units. The heated capillary was held at 200 1C.
MS spectra were obtained by applying a relative collision
energy of 25–40% of the instrumental maximum. (Spectra in
supplementary information.w)
Transmission electron microscopy (TEM) experiments were
performed directly in the IL media.21 A thin film of RuNP
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solution in IL was deposited on a carbon film supported by a

copper grid. Conventional TEM micrographs were obtained
at the ‘‘Centre Technologique des Microstructures’’, UCBL1,
Fig. 7 TEM image of RuNPs in IL1 after treatment with water and Villeurbanne, France, using a Philips 120 CX electron micro-
resultant size distribution histogram. scope with acceleration voltage of 120 kV. Size distribution
histograms were constructed from the measurement of at least
NPs must agglomerate, so preventing agglomeration has an 200 different nanoparticles assuming a near spherical shape
indirect influence on stability. and random orientation.
Conclusion GC analyses
The phenomenon of crystal growth of RuNPs generated in situ The products were quantitatively analysed by gas chromato-
from Ru(COD)(COT), in imidazolium-based ILs is found to graphy on a P6890 chromatograph equipped with a flame
be controlled by the size of non-polar domains created by the ionisation detector (FID) and an Al2O3/KCl column (L: 50 m,
grouping of lipophilic alkyl chains. Close proximity of the jint: 0.32 mm, film thickness: 5 mm). The injector and detector
RuNPs to the non polar R group of the cation is evidenced by temperature was 230 1C, and the injection volume was 1 mL.
in situ labelling experiments (deuteration and reduction), thus The temperature was fixed at 190 1C.
corroborating the hypothesis that RuNPs are surrounded by
these non-polar pockets. Addition of water, destroying the Hydrogenation of ethylene by RuNPs in the IL
ionic network, induces agglomeration of the RuNPs, supporting
A 2 mL sample of RuNP solution in IL was introduced under
the fact that the RuNPs are originally isolated within non-
argon into a Schlenk tube of known volume. The sample was
polar pockets by the 3-D network of ionic channels. Further-
treated under flow of argon for 18 h. The argon atmosphere
more, the presence of surface hydrides and their role in the
was replaced with a known pressure of ethylene using a
stabilisation of the nanoparticles is demonstrated. Finally, the
vacuum line and the system was stirred. A decrease of the
RuNPs are shown to be hydrophobic.
internal pressure was observed, and the composition of the gas
phase was monitored by gas chromatography. After 12 h, the
Experimental section atmosphere was replaced by a H2 atmosphere and the system
was heated and stirred for 12 h. The composition of the gas
All operations were performed in the strict absence of oxygen phase was again monitored by gas chromatography.
and water under a purified argon atmosphere using glovebox
(Jacomex or MBraun) or vacuum-line techniques. Imidazolium
H–D exchange
ionic liquids C4C1Im NTf2, IL1 C4//C1Im NTf2, IL2 BzC1Im
NTf2, IL3,39 Ru(COD)(COT),40 and RuNPs were synthesised A 2 mL sample of RuNP solution in IL was introduced under
as already reported.21,41 The halide content is under 200 ppm argon into a Schlenk tube, which was then treated under
(E.A), and water under 5 ppm, (limit of Karl Fischer titration). dynamic vacuum (10ÿ5 mbar) during a period of 1 or 4 h.
1-Methylimidazole (>99%) was purchased from Aldrich This was then charged with deuterium (1 bar) and stirred at
and distilled prior to use. Chlorobutane, benzyl chloride and 25 1C for a period of 1 or 4 d. The gas phase was subsequently
4-chlorobut-1-ene (>99%, Aldrich) were used without further expanded into an airtight Young tube for NMR analysis.
Acknowledgements 20 J. Dupont, G. S. Fonseca, A. P. Umpierre, P. F. P. Fichtner and
S. R. Teixeira, J. Am. Chem. Soc., 2002, 124, 4228–4229.
We would like to thank ANR CALIST and Ministe`re de 21 T. Gutel, J. Garcia-Anton, K. Pelzer, K. Philippot, C. C. Santini,
l’Enseignement Supe´rieur (P.S.C.) for financial support. Anne Y. Chauvin, B. Chaudret and J.-M. Basset, J. Mater. Chem., 2007,
17, 3290–3292.
Baudouin for 2H NMR experiments. 22 J. L. Anthony, J. L. Anderson, E. J. Maginn and J. F. Brennecke,
J. Phys. Chem. B, 2005, 109, 6366–6374.
23 R. Berthoud, P. Delichere, D. Gajan, W. Lukens, K. Pelzer,
Notes and references J.-M. Basset, J.-P. Candy and C. Coperet, J. Catal., 2008, 260,
1 (a) H. Bönnemann, K. S. Nagabhushana and R. M. Richards, 387–391; J. P. Candy, A. Elmansour, O. A. Ferretti, G. Mabillon,
in Nanoparticles and Catalysis, ed. D. Astruc, Wiley-VCH, J. P. Bournonville, J. M. Basset and G. Martino, J. Catal., 1988,
Weinheim, 2008; (b) M.-C. Daniel and D. Astruc, Chem. Rev., 112, 201–209.
2004, 104, 293–346. 24 R. Van Hardeveld and F. Hartog, Surf. Sci., 1969, 15, 189–230.
2 G. A. Somorjai and J. Y. Park, Top. Catal., 2008, 49, 126–135. 25 J.-M. Bassett, A. Baudouin, F. Bayard, J.-P. Candy, C. Copéret,
3 L. S. Ott and R. G. Finke, Coord. Chem. Rev., 2007, 251, A. de Mallmann, G. Godard, E. Kuntz, F. Lefebvre, C. Lucas,
1075–1100. S. Norsic, K. Pelzer, A. Quadrelli, C. Santini, D. Soulivong,
4 G. Schmid, Nanoparticles: From Theory to Application, Wiley- F. Stoffelbach, M. Taoufik, C. Thieuleux, J. Thivolle-Cazat and
VCH, Weinheim, 2004. L. Veyre, in Modern Surface Organometallic Chemistry,
5 (a) J. Dupont and D. d. O. Silva, in Nanoparticles and Catalysis, ed. ed. J. M. Basset, A. Psaro Rinaldo, A. Roberto Dominique and
D. Astruc, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, A. Ugo Renato, Wiley VCH, Weinheim, 2009, pp. 23–68.
2008, pp. 195–218; (b) A. Taubert and Z. Li, Dalton Trans., 2007, 26 M. Leconte, A. Theolier and J. M. Basset, J. Mol. Catal., 1985, 28,
723–727; (c) R. E. Morris, Angew. Chem., Int. Ed., 2008, 47, 217–231.
442–444; (d) J. Kraemer, E. Redel, R. Thomann and C. Janiak, 27 M. Leconte, A. Theolier, D. Rojas and J. M. Basset, J. Am. Chem.
Organometallics, 2008, 27, 1976–1978. Soc., 1984, 106, 1141–1142.
6 A. Corma, I. Dominguez, T. Rodenas and M. J. Sabater, J. Catal., 28 I. M. Ciobica, A. W. Kleyn and R. A. Van Santen, J. Phys. Chem.
2008, 259, 26–35. B, 2003, 107, 164–172.
tel-00708600, version 1 - 15 Jun 2012
7 A. P. Umpierre, G. Machado, G. H. Fecher, J. Morais and 29 T. H. Rod, A. Logadottir and J. K. Norskov, J. Chem. Phys., 2000,
J. Dupont, Adv. Synth. Catal., 2005, 347, 1404–1412. 112, 5343–5347.
8 L. S. Ott and R. G. Finke, Inorg. Chem., 2006, 45, 8382–8393. 30 J. Wang, C. Y. Fan, Q. Sun, K. Reuter, K. Jacobi, M. Scheffler and
9 L. S. Ott, M. L. Cline, M. Deetlefs, K. R. Seddon and R. G. Finke, G. Ertl, Angew. Chem., Int. Ed., 2003, 42, 2151–2154.
J. Am. Chem. Soc., 2005, 127, 5758–5759. 31 M. P. Stracke, M. V. Migliorini, E. Lissner, H. S. Schrekker,
10 T. Gutel, C. C. Santini, K. Philippot, K. Pelzer, Agilio Padua, D. Back, E. S. Lang, J. Dupont and R. S. Gonçalves, New J.
B. Chaudret, Y. Chauvin and J.-M. Basset, J. Mater. Chem., 2009, Chem., 2009, 33, 82–87.
19, 3624–3631. 32 A. Roucoux, A. Nowiki and K. Philippot, in Nanoparticles,
11 A. A. H. Padua, M. F. Costa Gomes and J. N. A. Canongia Lopes, ed. D. Astruc, Wiley-VCH, Weinheim, 2007.
Acc. Chem. Res., 2007, 40, 1087–1096. 33 L. Cammarata, S. G. Kazarian, P. A. Salter and T. Welton, Phys.
12 M. G. Del Popolo, C. L. Mullan, J. D. Holbrey, C. Hardacre and Chem. Chem. Phys., 2001, 3, 5192–5200.
P. Ballone, J. Am. Chem. Soc., 2008, 130, 7032–7041. 34 J. N. Canongia Lopes, M. F. Costa Gomes and A. A. H. Padua,
13 T. Gutel, C. C. Santini, A. A. H. Padua, B. Fenet, Y. Chauvin, J. Phys. Chem. B, 2006, 110, 16816–16818.
J. N. Canongia Lopes, F. Bayard, M. F. Costa Gomes and 35 Y.-Y. Jiang, Z. Zhou, Z. Jiao, L. Li, Y.-T. Wu and Z.-B. Zhang,
A. S. Pensado, J. Phys. Chem. B, 2009, 113, 170–177. J. Phys. Chem. B, 2007, 111, 5058–5061.
14 K. Pelzer, O. Vidoni, K. Philippot, B. Chaudret and V. Collière, 36 A. Mele, C. D. Tran and S. H. De Paoli Lacerda, Angew. Chem.,
Adv. Funct. Mater., 2003, 13, 118–126. Int. Ed., 2003, 42, 4364–4366.
15 K. Philippot and B. Chaudret, C. R. Chimie, 2003, 6, 37 A.-L. Rollet, P. Porion, M. Vaultier, I. Billard, M. Deschamps,
1019–1034. C. Bessada and L. Jouvensal, J. Phys. Chem. B, 2007, 111,
16 T. Pery, K. Pelzer, G. Buntkowsky, K. Philippot, H.-H. Limbach 11888–11891.
and B. Chaudret, ChemPhysChem, 2005, 6, 605–607. 38 B. L. Bhargava and M. L. Klein, J. Phys. Chem. B, 2009, 113,
17 J. Garcia-Anton, M. R. Axet, S. Jansat, K. Philippot, B. Chaudret, 9499–9505.
T. Pery, G. Buntkowsky and H.-H. Limbach, Angew. Chem., Int. 39 L. Magna, Y. Chauvin, G. P. Niccolai and J.-M. Basset, Organo-
Ed., 2008, 47, 2074–2078. metallics, 2003, 22, 4418–4425.
18 C. Pan, K. Pelzer, K. Philippot, B. Chaudret, F. Dassenoy, 40 P. Pertici, G. Vitulli, M. Paci and L. Porri, J. Chem. Soc., Dalton
P. Lecante and M.-J. Casanove, J. Am. Chem. Soc., 2001, 123, Trans., 1980, 1961–1964.
7584–7593. 41 T. Gutel, C. C. Santini, K. Philippot, A. A. H. Padua, K. Pelzer,
19 K. Pelzer, K. Philippot and B. Chaudret, Z. Phys. Chem., 2003, B. Chaudret, Y. Chauvin and J.-M. Basset, J. Mater. Chem., 2009,
217, 1539–1547. 19, 3624–3631.
This journal is
8156 J. Phys. Chem. B 2010, 114, 8156–8165
How do Physical-Chemical Parameters Influence the Catalytic Hydrogenation of

1,3-Cyclohexadiene in Ionic Liquids?
Paul S. Campbell,† Ajda Podgoršek,‡ Thibaut Gutel,† Catherine C. Santini,*,†

Agı́lio A. H. Pádua,‡,§ Margarida F. Costa Gomes,*,‡,§ François Bayard,† Bernard Fenet,| and
Yves Chauvin†
UniVersité de Lyon Institut de Chimie de Lyon, UMR 5265 CNRS-UniVersité de Lyon 1-ESCPE Lyon,
C2P2, Equipe Chimie Organométallique de Surface, ESCPE 43 BouleVard du 11 NoVembre 1918,
F-69616 Villeurbanne, France, Laboratoire de Thermodynamique et Interactions Moléculaires, CNRS, UMR
6272 24 AVenue des Landais, 63177 Aubière, France, Clermont UniVersité and UniVersité Blaise Pascal,
Clermont-Ferrand, France, and Centre Commun de RMN, UCB Lyon 1 - ESCPE Lyon, 43 BouleVard du 11
NoVembre 1918, F-69626 Villeurbanne Cedex, France
ReceiVed: April 1, 2010; ReVised Manuscript ReceiVed: May 11, 2010
The catalytic hydrogenation of 1,3-cyclohexadiene using [Rh(COD)(PPh3)2]NTf2 (COD ) 1,5-cyclooctadiene)

was performed in two ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,
[C1C4Im][NTf2], and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [C1C1C4Im][NTf2].
It is observed that the reaction is twice as fast in [C1C4Im][NTf2] than in [C1C1C4Im][NTf2]. To explain the
tel-00708600, version 1 - 15 Jun 2012
difference in reactivity, molecular interactions and the microscopic structure of ionic liquid +1,3-cyclohexadiene
mixtures were studied by NMR and titration calorimetry experiments, and by molecular simulation in the
liquid phase. Diffusivity and viscosity measurements allowed the characterization of mass transport in the
reaction media. We could conclude that the diffusivity of 1,3-cyclohexadiene is 1.9 times higher in
[C1C4Im][NTf2] than in [C1C1C4Im][NTf2] and that this difference could explain the lower reactivity observed
in [C1C1C4Im][NTf2].
1. Introduction solutes are solvated in the ionic liquid:14 nonpolar species will
be solvated within the hydrophobic domains whereas polar
The application of ionic liquids (ILs) in catalyzed reactions
substrates tend to interact with the polar network. The strength
is of increasing importance,1,2 in particular, they provide
of cation-anion association15 can also influence the possibility
excellent media for conducting catalytic hydrogenations.1-3
of establishing ion-solute specific interactions (e.g., π-cation
Several research groups report differences in the rates and
interactions), as has been shown in the case of toluene.9 For a
selectivities in ILs when compared to corresponding reactions
nonaromatic π-system, such as 1,3-cyclohexadiene, solvation
in molecular solvents.2
is probably a combination of more subtle interactions with the
As reaction media, ILs have specific properties that may have
ionic liquid. This information can be assessed through the study
consequences on the catalytic process. In some catalytic
of the thermodynamic properties of solution (solubility, enthalpy
reactions, the difference between the use of ILs and traditional
of solution) and from the characterization of the mass transfer
solvents has been related to the chemical role of ILs, which can
through viscosity and diffusivity data.
serve as new ligands for the catalytic metal center, as catalyst
The aim of this work is to study the influence of the nature
activators, as cocatalysts, or even as catalysts themselves.1,4,5 In
of the ionic liquid on the catalytic hydrogenation of 1,3-
other cases, differences in reactivity have a physical-chemical
cyclohexadiene (CYD) with [Rh(COD)(PPh3)2]NTf2 (COD )
origin,1,6 resulting from peculiar solvation phenomena including
1,5-cyclooctadiene). First, we have quantified the difference in
specific interactions between the IL and the substrate (H-bonds,
reactivity when the reaction is performed in two ionic liquids:
cation-π),7-9 mass transfer factors (viscosity, diffusivity),1 and
1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,
effects attributed to the highly structured nature of ILs.10-12
[C1C4Im][NTf2], and 1-butyl-2,3-dimethylimidazolium bis(tri-
ILs have a high degree of self-organization due to the fluoromethylsulfonyl)imide, [C1C1C4Im][NTf2]. Following this,
coexistence of charged moieties and hydrophobic alkyl chains, we have attempted to rationalize the differences encountered
to the importance of both Coulombic and van der Waals through NMR characterization of the molecular interactions
interactions, and frequently to the presence of hydrogen bonds between the ionic liquids and the substrate, the study of the
between the cation and the anion. In butylimidazolium ionic microscopic structure of the IL-substrate mixtures, the measure-
liquids, the alkyl side chain is sufficiently long to allow the ment of the thermodynamic properties of mixing (such as the
formation of nonpolar domains that coexist with an ionic solubility and the heat of mixing), the determination of the
network.13 This heterogeneous structure influences the way viscosity of the reaction media, and the measurement of
diffusivity of CYD in the ionic liquids.
* To whom correspondence should be addressed. E-mail: C.C.S., santini@
cpe.fr; M.F.C.G., margarida.costa-gomes@univ-bpclermont.fr.
†
Université de Lyon. 2. Experimental Section
‡
CNRS.
§
Clermont Université and Université Blaise Pascal. Materials. 1-Methylimidazole (>99%, Aldrich) and 1,2-
|
Centre Commun de RMN. dimethylimidazole (>98%, Aldrich) were distilled prior to use.
10.1021/jp102941n  2010 American Chemical Society
Published on Web 05/26/2010
Catalytic Hydrogenation of 1,3-Cyclohexadiene J. Phys. Chem. B, Vol. 114, No. 24, 2010 8157
Anhydrous 1,3-cyclohexadiene (99.8%, Aldrich) and 1,3- in presence of toluene as an internal standard. A HP6890
cyclohexadiene stabilized (96%, Acros Organics, stabilized with chromatograph equipped with FID detector and an Al2O3/KCl
50 ppm of 2,6-di-tert-butyl-4-methylphenol, BHT) distilled over column (L ) 50 m, φint ) 0.32 mm, film thickness ) 5 µm)
NaK alloy and stored on zeolites were used for the reaction was used. The injector and detector temperatures were set to
and the physical chemical measurements, respectively. Bis(tri- 230 °C. Samples were injected in a volume of 1 µL. The
fluoromethanesulfonyl)imide lithium salt (>99%, Solvionic) and temperature of the column was fixed at 190 °C (see Supporting
[Rh(COD)Cl]2 (>99%, Strem) were used without further puri- Information for calculations).
fication. All other reagents and solvents were commercially Solubility and Phase Diagrams. Liquid-liquid phase equi-
available and were used as received. Ionic liquids, synthesized libria of the mixture of [C1C4ImNTf2] or [C1C1C4Im][NTf2] and
as previously reported,16 were dried overnight under high CYD at atmospheric pressure were determined using a dynamic
vacuum and stored in a glovebox (Jacomex) to guarantee method with visual detection of solution turbidity, as already
rigorously anhydrous products. described.18
Synthesis of the Catalysts. [Rh(COD)(PPh3)2]NTf2. The The mixtures of ionic liquid and CYD at different composi-
procedure followed was adapted from the literature.17 A mixture tions were prepared gravimetrically in a glass vial equipped with
of [Rh(COD)Cl]2 (100 mg, 0.2 mmol) dissolved in 2 mL of a stirring bar. First, the ionic liquid was introduced into a glass
dichloromethane and of LiNTf2 (107 mg, 0.37 mmol) dissolved vial, then the appropriate amount of CYD was added and the
in 2 mL of water was stirred vigorously while triphenylphos- vial was sealed. To minimize the volume of the vapor phase in
phine (405 mg, 1.5 mmol) was added. After 2 h, the dichlo- equilibrium with the ionic liquid solution and to reduce the error
romethane layer was removed, washed three times with 2 mL in composition due to differential evaporation, the glass vial
of water and dried over anhydrous Na2SO4. Ethanol (1 mL) and was almost completely filled with the mixture. The uncertainty
diethyl ether (2 mL) were slowly added to complete crystal- of the mole fraction is estimated as (0.0001. The cells were
lization. The orange crystals were filtered off and dried under then immersed in a thermostatic water bath whose temperature
reduced pressure. Yield: 200 mg (99%). 1H NMR (300 MHz, was monitored using a platinum resistance thermometer with a
tel-00708600, version 1 - 15 Jun 2012
CD2Cl2): δ ) 2.2 (m, 8H), 4.6 (s, 4H), 7.5 (m, 30H). 31P NMR precision of (0.1 K. The temperature of the bath was first
(121 MHz, CD2Cl2): δ ) 23.6 with JRh-P ) 147 Hz. 103Rh NMR increased slowly until one phase was observed. The clear
(500 MHz, CD2Cl2): δ ) -80 ppm with JRh-P ) 147 Hz. Mass homogeneous system was then cooled very slowly (5 K/h) under
spectrometry: positive mode: m/z ) 473 w Rh(COD)(PPh3)+; continuous stirring. The temperature at which the first sign of
627 w Rh(PPh3)2+. UV-vis spectroscopy (6.6 mg of turbidity (first cloudiness) appeared was considered as the
[Rh(COD)(PPh3)2]NTf2 dissolved in 2 mL of one of ionic temperature of the liquid-liquid phase transition. The overall
liquids, [C1C4Im][NTf2] or [C1C1C4Im][NTf2]); spectrum re- accuracy in the measurement of cloud-point temperatures is
corded at λmax ) 450 nm. estimated to be (2 K.
[Rh(CYD)(PPh3)2]NTf2. [Rh(COD)(PPh3)2]NTf2 (100 mg, Isothermal Titration Calorimetry. The heat effects resulting
9.84 × 10-5 mol) was dissolved in 1 mL of CYD. After 10 from mixing aliquots of CYD with the ionic liquid were
min, the excess of solvent was removed under reduced measured at 303.15 K using an isothermal titration nanocalo-
pressure. Yield: 100 mg (99%). 1H NMR (300 MHz, CD2Cl2): rimeter equipped with 4 mL glass cells in a Thermal Activity
δ ) 2.1 (s, 2H), 5.3 (s, 2H), 7.5 (m, 30H). 31P NMR (121 Monitor TAM III from TA Instruments. An electrical calibration
MHz, CD2Cl2): δ ) 25.2 ppm with JRh-P ) 17 Hz. Mass was done before each experiment, and the instrument was
spectrometry: positive mode: m/z ) 707 w Rh(cyclohex- chemically calibrated 5 times by titration of a 0.01 M aqueous
adiene)(PPh3)2+; m/z ) 627 w Rh(PPh3)2+. UV-vis spec- solution of 18-crown-6 ethers with an 0.2 M aqueous solution
troscopy (6.6 mg of [Rh(CYD)(PPh3)2]NTf2 dissolved in 2 mL of of BaCl2. The enthalpies of binding of Ba2+ ions to 18-crown-6
one of ionic liquids, [C1C4Im][NTf2] or [C1C1C4Im][NTf2]); were found to be slightly higher than those reported in the
spectrum recorded at λmax ) 500 nm. literature, 2.5%19 and 1.6%,20,21 respectively. No correction
Ligand Exchange. In [Rh(CYD)(PPh3)2]NTf2 was followed attributable to these differences was introduced in the raw data.
by UV-vis spectroscopy. CYD (0.15 mL, 1.6 mmol) was added Approximately 2.75 mL of degassed ionic liquid were
to a system of [Rh(COD)(PPh3)2]NTf2 (1.6 mg, 1.6 µmol) in introduced into 4 mL glass measuring and reference cells. The
one of the ionic liquids, [C1C4Im][NTf2] or [C1C1C4Im][NTf2] liquid in the measuring cell was stirred by a turbine stirrer at
(1 mL). The UV-visible spectra of 1 mL of the solution were 160 rpm and volumes of 4 µL of CYD were injected during
recorded on the Perkin-Elmer LAMBDA 950 Spectrophotometer 180 s using a motor driven pump (Thermometric 3810 Syringe
in stirred and closed UV cells at λmax ) 500 nm every second. Pump) equipped with a 100 µL gastight Hamilton syringe. In
Reaction with H2. [Rh(CYD)(PPh3)2]NTf2 (8 mg, 8.1 × 10-6 all experiments, the intervals between consecutive injections
mmol) was dissolved in one of the ionic liquids, [C1C4Im][NTf2] were 35-40 min, which provided a good thermal stabilization
or [C1C1C4Im][NTf2] (5 mL) and pressurized under 1.2 bar of of the ionic liquid solution and the return to a stable baseline.
hydrogen. The UV-visible spectra of 1 mL of the solution were To minimize the undesirable effects of diffusion of the ionic
recorded at a given time at λmax ) 500 nm. liquid into the canula linking the CYD syringe to the cell, the
Hydrogenation of 1,3-Cyclohexadiene. The hydroge- canula was immersed in the sample 10 min prior the first
nation of CYD was carried out at 1.2 atm of H2 and 30 °C. injection.
CYD (0.15 mL, 1.6 mmol) was dissolved in a system of A peak with an area proportional to the resulting heat effect
[Rh(COD)(PPh3)2]NTf2 (3.2 mg, 3.2 µmol) in one of ionic Qi translates to the thermal effect due to each injection of CYD.
liquids, [C1C4Im][NTf2] or [C1C1C4Im][NTf2] (1 mL), under The integration of peaks from the recorded calorimetric plots
argon resulting in red homogeneous solutions. The reaction was performed using the TAM III Assistant software. Each
mixture was kept under a hydrogen atmosphere (1.2 atm, experiment was repeated four times to obtain reproducible values
constant pressure) until 4 mL of acetonitrile was added to the of Qi at different concentrations within the error bar of (2%.
catalytic solution. The product distribution in the reaction Density and Viscosity. The mixtures of ionic liquid and CYD
mixture and the conversion were determined by GC analyses at different compositions were prepared gravimetrically follow-
8158 J. Phys. Chem. B, Vol. 114, No. 24, 2010 Campbell et al.
ing the procedure already described, including the precautions gradients to improve line shape and trapezoidal gradients (the
to minimize vapor headspace.9 The viscosity of the mixture was pulse sequences shown in Figure S-6 in Supporting Information).
measured at 298.15 K (controlled to within (0.005 K and The diffusion evolution time was 100 ms, the constant amplitude
measured with the accuracy better than (0.05 K) using a rolling part of the gradient was 3 ms, and the cosine raising and falling
ball viscometer from Anton Paar, model AMVn, equipped with part of gradient were 150 µs. The diffusion space was sampled
capillary tubes of 3.0 and 1.8 mm in diameter. Before starting by 32 linearly spaced gradients.
the measurements, the 3.0 mm diameter capillary tube was Molecular Simulation. The microscopic structures of the IL-
calibrated as a function of temperature and angle of measure- CYD mixtures studied experimentally were also investigated
ment with a standard viscosity oil from Cannon (N35). The 1.8 by molecular simulation, using an atomistic force field that
mm diameter tube was calibrated with water by the manufac- describes interactions and conformations.23-25 CYD was rep-
turer. The overall uncertainty of the viscosity is estimated as resented by the optimized potential for the liquid simulations
(2.0%. force field in its all-atom explicit version (OPLS-AA).26 ILs
The densities of the mixtures, necessary to calculate the were represented by a specifically parametrized force field of
viscosities were measured in an Anton Paar vibrating tube the OPLS-AA family in which particular attention was paid to
densimeter model 512 P, at 298.15 K (measured by a calibrated the description of electrostatic charge distributions and torsion
PRT with an accuracy of (0.02 K). The densimeter was energy profiles. The OPLS-AA force field is known to reproduce
calibrated using n-heptane, bromobenzene, and 2,4-dichloro- H-bonds well; the electron density of aromatic systems is
toluene. The overall uncertainty of the density is estimated as represented by the values of electrostatic charges on the relevant
(0.01%. atoms that account for the molecular mutipoles, combined with
NMR Spectroscopy. 1H, 13C, and 31P solution NMR data the Lennard-Jones sites that account for dispersion interactions.
were collected at room temperature on a Bruker AC 300 MHz Explicit polarization of electron clouds is not included in the
spectrometer with the resonance frequency at 300.130 MHz for present model. Although this may be important to correctly
the 1H nucleus. 103Rh solution NMR was carried out on a Bruker reproduce dynamic properties of ILs, structural features and
tel-00708600, version 1 - 15 Jun 2012
DRX 500 instrument at 298 K (nominal) with a resonance thermodynamic quantities have been described to equivalent
frequency at 500.130 MHz. The solvent used (CD2Cl2) was levels of accuracy using fixed-charge models.27
distilled and kept in a rotaflo with molecular sieves. Chemical Molecular dynamics simulations of condensed-phase CYD-
shifts are reported in ppm (singlet ) s, doublet ) d, doublet of [C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2] mixtures were
doublet ) dd, and multiplet ) m) and were measured relative performed using the DL_POLY program.28 System sizes were
to the residual proton of the solvent to CHDCl2 for 1H, to CD2Cl2 chosen so as to contain about 10 000 atoms, and so the numbers
for 13C, and to H3PO4 for 31P spectra. of cations, anions, and CYD molecules varied according to
For 1H 1D NMR spectroscopy, the samples with molar ratio composition (e.g., 128 ion pairs and 64 molecules of CYD for
R ) 0.5). Initial low-density configurations, with ions and
R ) 0.5 (R is the molar ratio between the amount of substance
molecules placed at random in periodic cubic boxes, were
of the hydrocarbon and the amount of substance of IL) were
equilibrated to attain liquid-like densities and structures at 400
prepared. The mixtures of ionic liquids and hydrocarbon were
K and 1 bar. Temperature and pressure were maintained using
prepared in closed vials in a glovebox by adding the appropriate
a Nosé-Hoover thermostat and barostat, respectively. Produc-
amount of CYD to each ionic liquid, [C1C4Im][NTf2] or
tion runs then took 500 ps with an explicit cutoff distance of
[C1C1C4Im][NTf2]. The resulting systems were stirred for 24 h
16 Å for nonbonded interactions, and long-range corrections
at 303 K, resulting in homogeneous monophasic solutions.
applied for repulsive-dispersive interactions. Electrostatic ener-
Approximately 0.3 mL of the sample was then introduced into
gies were calculated using the Ewald summation method with
a 5 mm NMR tube. A stem coaxial capillary tube loaded with
a relative accuracy of 10-4. Structural quantities such as radial
CD2Cl2 was inserted into the 5 mm NMR tube to avoid any
and spatial distribution functions were calculated from configu-
contact between the deuterated solvent and the analyzed mixture.
rations generated during the production runs.
The deuterium in CD2Cl2 was used for the external lock of the
NMR magnetic field and the residual CHDCl2 in CD2Cl2 was
used as the 1H NMR external reference at 5.32 ppm. When 1H 3. Results and Discussion
NMR data are obtained in this way, the reference signal of Hydrogenation of 1,3-Cyclohexadiene. Selective hydroge-
CHDCl2 remains constant and is not affected by changes in nation of CYD into cyclohexene can be carried out, with good
sample concentration. conversion rates, using Osborn’s complex [Rh(NBD)(PPh3)2]PF6
For ROESY (nuclear overhauser effect spectroscopy) experi- (NBD ) norbornadiene) in IL media such as [C1C4Im][SbF6]
ments in the rotating frame, the 2D sequence was built with or [C1C4Im][PF6].29 To avoid impurities such as chloride and
the scheme proposed by Bodenhausen (the pulse sequence water, ILs based on the bis(trifluoromethylsulfonyl)imide anion,
shown in Figure S-3 in Supporting Information).22 The mixing [C1C4Im][NTf2] and [C1C1C4Im][NTf2], were chosen here since
time (200 ms) is split into two parts separated by a p-pulse. At they are hydrophobic and liquid at room temperature and their
each side of the spin lock the B1 field is ramped linearly (4.5 purification is well controlled.16 Anion exchange between the
ms) to ensure adiabatic conditions for spin lock. During the IL and the catalyst can be circumvented by replacing Osborn’s
first spin lock pulse, the frequency is shifted to O1 + Df whereas complex with [Rh(COD)(PPh3)2]NTf2 (COD ) 1,5-cycloocta-
the second pulse frequency is set to O1 - Df; O1 is the offset diene).
frequency and Df set to give a B1 field at the magic angle. In In the hydrogenation experiment the appropriate quantity of
this way, the ROESY response is roughly constant across the CYD was added to the yellow solution of [Rh(COD)(PPh3)2]-
spectra of interest. 1D sequence PFGSE (pulse field gradient NTf2 in [C1C4Im][NTf2] or [C1C1C4Im][NTf2] to reach a molar
spin echo for selective excitation) has been used, and spin lock ratio between CYD and IL R ) 0.5, corresponding to a molar
followed the same scheme as previously. ratio substrate/Rh atom r ) 500. The resulting red solution was
For the 2D DOSY (diffusion order spectroscopy) experiments stirred under 1.2 bar of hydrogen at 303 K. The formation of
a Bruker sequence ledbpgp2s was implemented for shorter pulse cyclohexene (CYE) was followed by GC analysis. Note that
Figure 1. Hydrogenation of CYD at 303 K under 1.2 bar H2 (R ) 0.5 Figure 2. Evolution as a function of time of the ligand exchange
and r ) n(CYD)/n(Rh) ) 500) in [C1C4Im][NTf2] ([) and reaction COD-CYD for [Rh(COD)(PPh3)2]NTf2 in [C1C4Im][NTf2]
[C1C1C4Im][NTf2] (b). (full line) and [C1C1C4Im][NTf2] (dashed line) monitored at λ ) 500
nm by UV-vis spectroscopy. UV-visible spectra of [Rh(COD)(PPh3)2]-
NTf2 and [Rh(CYD)(PPh3)2]NTf2 are provided in the Supporting
CYE is less soluble than CYD in both IL media so the system Information (Figures S-1 and S-2).
will tend to become biphasic during the course of the reaction.
tel-00708600, version 1 - 15 Jun 2012
To avoid errors in the determination of the composition of the

reaction mixture, resulting from heterogeneity of the system,
the conversion was measured using GC analysis of the entire
reaction system after dissolution in a mixture of acetonitrile and
toluene 99:1. Each point, presented in Figure 1, corresponds to
a different experiment.
As can be seen in Figure 1, hydrogenation of CYD in both
ILs by [Rh(COD)(PPh3)2]NTf2 leads quantitatively and selec-
tively to CYE. In both cases, no significant amount (less than
2% at high or complete conversion) of cyclohexane (CYH) was
detected by GC. As described in the literature, the rate of CYD
reduction remains constant until near 100% conversion (1 mol
of H2 absorbed per CYD) and CYE is produced quantitatively
before it is hydrogenated to CYH.17 In [C1C4Im][NTf2] the
conversion is complete in 2 h. This result is similar to that
observed in organic solvents17 and in other ionic liquids, such
as [C1C4Im][PF6] or [C1C4Im][SbF6].29 In [C1C1C4Im][NTf2], Figure 3. Evolution of the absorbance at λ ) 500 nm as a function of
only 50% conversion is reached after 2 h with an initial rate of time during the hydrogenation reaction of CYD in the presence of
hydrogenation ca. half of that in [C1C4Im][NTf2]. [Rh(CYD)(PPh3)2]NTf2 in [C1C4Im][NTf2] ([) and [C1C1C4Im][NTf2]
In organic solvents, during the hydrogenation of 1,3-cyclo- (b).
hexadiene, the catalyst first undergoes a ligand exchange,
yielding [Rh(CYD)(PPh3)2]+. This occurs more rapidly than the
organic solvents, ligand exchange is faster than hydrogenation.
rate at which it then reacts with H2.30 The two reaction steps
More importantly, the rate at which the CYE is produced (Figure
were investigated in both ILs. First, [Rh(CYD)(PPh3)2]NTf2 was
synthesized from [Rh(COD)(PPh3)2]NTf2 and fully character- 1) is similar to the rate of discoloration due to attack of
ized. As [Rh(COD)(PPh3)2]NTf2 is yellow (λmax ) 450 nm) and [Rh(CYD)(PPh3)2] by H2 (Figure 3). Consequently, in ac-
[Rh(CYD)(PPh3)2]NTf2 is red (λmax ) 500 nm), the ligand cordance with the literature,30 in the hydrogenation of CYD,
exchange COD-CYD could be monitored by UV-vis spectros- this attack is the rate-determining step.
copy (λ ) 500 nm) in both ILs, as shown in Figure 2. This As solubilities of H2 are similar in both ionic liquids,31 the
reaction is also much slower in [C1C1C4Im][NTf2] than in same overall rate of reaction would be expected. However, this
[C1C4Im][NTf2]. is not the case and could be attributed to differences in the
Secondly, the red solutions of [Rh(CYD)(PPh3)2]NTf2 in availability of H2 in the different media. Indeed, even though
[C1C4Im][NTf2] or [C1C1C4Im][NTf2] were exposed to hydrogen no literature data are available for H2 in ILs, it is generally found
and the color disappeared with the concomitant formation of that the diffusion of gases is inversely dependent on the viscosity
CYE. This hydrogenation reaction of CYD in [Rh(CYD)(PPh3)2]- of the medium.32 Because the same difference in the rate of
NTf2 was also monitored by UV-vis spectroscopy in both ILs, reaction is noted in the ligand exchange, where H2 is not
the absorbances being represented in Figure 3. The discoloration involved, the differences in the inherent properties of each IL
of the medium, indicating the hydrogenation step, is also faster must be considered. For instance, studies by molecular simula-
in [C1C4Im][NTf2] than in [C1C1C4Im][NTf2]. These results tions and NMR of solvation and molecular structure of similar
indicate that both ligand exchange and hydrogenation reactions mixtures showed that according to the nature of the IL, specific
are faster in [C1C4Im][NTf2]. These processes, however, do not interactions with the solute differ.7-9 In addition, mass transport
occur on the same time scale (hours versus seconds) and, as in factors (viscosity, diffusivity) have also been related to the
Figure 4. Liquid-liquid equilibrium diagrams for the mixture of CYD

and [C1C4Im][NTf2] (b) or [C1C1C4Im][NTf2] ([) and solubility of Figure 5. Partial molar excess enthalpies vs mole fraction of CYD in
toluene in [C1C4Im][NTf2] (]) or [C1C1C4Im][NTf2] (O). the binary mixture with [C1C4Im][NTf2] ([) or [C1C1C4Im][NTf2] (b)
E
at 303.15 K. The lines represent functions: HCYD ) 1.6285 +
E
0.2481xCYD (b) and HCYD ) 0.8574 - 0.1518xCYD ([).
reactivity1,33 and therefore are also important parameters that
we will determine and discuss here.
molar enthalpy. We have done so for both systems, CYD-
Solvation of 1,3-Cyclohexadiene. Figure 4 shows cloud-point
[C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2]. The excess
tel-00708600, version 1 - 15 Jun 2012
temperatures as a function of composition for [C1C4Im][NTf2]- E

molar enthalpy of mixing ∆Hmix was determined by isothermal
CYD and [C1C1C4Im][NTf2]-CYD.18,34 The observation of the
titration calorimetry, from the heat effect involved in injections
cloud point with decreasing temperature was difficult, especially
of small quantities of CYD into the ionic liquid, QCYD. The
for the [C1C1C4Im][NTf2]-CYD system, because in this case E
partial molar excess enthalpy of solute, HCYD , was calculated
the mixtures often remained in a metastable state and cloudiness
according to eq 1.
persisted despite overheating. The observation of the cloud point
while decreasing the temperature was not reproducible during
( )
E
this experiment, mainly because of the effect of precooling and E
∂∆Hmix QCYD
kinetics of demixing, as already discussed,33 and consequently HCYD ) ≈ (1)
∂nCYD nIL,p,T ∆nCYD
the solubility was determined at only two temperatures. Deter-
mination of the solubility of CYD in ionic liquids by liquid-vapor
equilibria measurements using a static apparatus35,36 was not where nCYD and nIL denote the quantity of CYD and IL,
E
possible due to the chemical properties of CYD, such as its respectively, ∆Hmix is the excess molar enthalpy of the entire
tendency to polymerize37 and its compatibility with o’ring system (enthalpy of mixing) and ∆nCYD is the quantity of solute
materials. per injection. ∆nCYD was calculated from the injected volumes
The solubility of CYD at 303.15 K, expressed in mole fraction and the density of CYD was obtained from the literature.40 In
is 0.42 in [C1C4Im][NTf2] and 0.34 in [C1C1C4Im][NTf2] (see these calculations, heat due to evaporation of the solute from
Figure 4), which could indicate less favorable interactions IL solution is assumed to be negligible. Hence, no correction
between CYD and the [C1C1C4Im] ion in comparison with the for the vapor pressure of the solute was made.
[C1C4Im] ion. In the temperature range studied, both systems Figure 5 represents partial molar excess enthalpies of CYD
CYD-[C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2] show a in both ILs at 303.15 K as a function of composition. A larger
behavior compatible with the existence of upper critical solution dispersion of the values (up to 3%), especially at higher
temperatures and very steep liquid-liquid equilibrium lines. concentration, was observed. At times, before each injection of
With this method the solubility of the ionic liquid in CYD could CYD into the IL, an exothermic effect was detected, mainly
not be detected, as it lies below the limit of detection. From originating from insufficient mixing of both components at the
measurements and from calculations using COSMO-RS,38 it is beginning of the injection period. As already discussed in the
known that the concentration of hydrocarbons in the ionic liquid literature41 in the case of aromatic hydrocarbons, the rate of
rich phase is very low, with mole fractions on the order of 10-4. dissolution of nonpolar, low density and low viscosity CYD in
In comparison with aromatic molecules in these ILs, CYD is the IL is slow and sometimes leads to formation of a solute-
much less soluble. For instance, the solubility of toluene at rich layer on the surface of the solution. This is often
303.15 K expressed in mole fraction is 0.73 in [C1C4Im][NTf2] accompanied by partial evaporation or even polymerization of
and 0.72 in [C1C1C4Im][NTf2],9 the solubility of benzene in CYD before the mixing process is complete, hence disturbing
[C1C4Im][NTf2] being even higher (mole fraction of 0.78 at the measurements. A large number of injections were made to
303.15 K).39 The small difference in solubility of toluene with ensure reliability. [The formation of a polymer was observed
respect to benzene can be attributed to the presence of an and confirmed by NMR analysis.37 This side reaction is
additional methyl group, whereas the much lower solubility of attributed to the fact that CYD has been distilled to eliminate
CYD is explained by less favorable interactions between the the stabilizer BHT before the physical chemical measurements.]
solute and the ILs. Disruption of the aromatic system changes The dependence of partial molar excess enthalpy of CYD in
the interactions between solute and ionic liquid and thus [C1C4Im][NTf2] and [C1C1C4Im][NTf2] on the mole fraction was
decreases the solubility. approximated by a linear regression, eq 2 and Figure 5. The
The energy involved in the interactions of different solutes partial excess molar enthalpies of CYD in both ILs at infinite
E,∞
dissolved in ILs can be assessed by measuring the excess dilution, HCYD , were obtained from eq 2 by setting xCYD ) 0
E
ane in [C1C2Im][NTf2]. As expected, the values of ∆Hmix for
CYD obtained here are intermediate between the values for
cyclohexene and benzene. Comparison of [C1C4Im][NTf2] and
[C1C1C4Im][NTf2] shows that introduction of an additional
methyl group on the C2 carbon of the imidazolium ring strongly
affects the interaction with molecules of CYD, which becomes
less favorable. To rationalize the differences in the solvation of
CYD in both ILs, and to complement the enthalpic data with
structural information, the microscopic structure of the mixtures
was investigated using NMR and molecular simulation.
Molecular Structure of the Reaction Media. The molecular
structure of the mixture of CYD and ILs, [C1C4Im][NTf2] and
[C1C1C4Im][NTf2], and therefore the sites of specific interactions
were studied by 1H NMR and ROESY experiments. The 1H
NMR chemical shifts of the CYD-IL mixtures at R ) 0.5 were
not significantly different from those of the neat CYD and ILs,
in both cases (Table S-1 in Supporting Information).
Figure 6. Excess molar enthalpies of the systems: CYD-[C1C4Im]-
[NTf2] (s) and CYD-[C1C1C4Im][NTf2] (---) vs the mole fraction of NOESY experiments exhibited very weak or null cross peak
CYD at 303.15 K. intensities. This was probably due to the fact that the quantity
ωτc was such that the NOE intensity was close to the null point.
TABLE 1: Excess Molar Enthalpies of Mixing of Organic Rotating frame NOE experiments (ROESY) allowed us to obtain
Solutes and Ionic Liquids at Mole Fraction of Solute 0.1
positive NOEs irrespective of the long rotational correlation time
E
ionic liquid solute ∆Hmix (J/mol) T (K) due to the high viscosity of the system. In 1H-1H ROESY
tel-00708600, version 1 - 15 Jun 2012
[C1C4Im][NTf2] 1,3-cyclohexadiene +85 ( 9 303.15 techniques based on space cross relaxations, the selective
[C1C1C4Im][NTf2] 1,3-cyclohexadiene +164 ( 10 303.15 irradiation of a proton group affects the intensities of integrals
[C1C4Im][NTf2] benzene -189.842 363.15 of all proton groups that are spatially close but not necessarily
[C1C4Im][NTf2] toluene -150.440 363.15 connected by chemical bonds. The method is based on the
[C1C4Im][NTf2] methylcyclohexane +435.640 363.15 assumption of short-range intermolecular distances (4-5 Å).43
[C1C2Im][NTf2] benzene -112.734 323.15
[C1C2Im][NTf2] toluene -115.639 298.15 The strength of the ROE signal is proportional to the inverse
[C1C2Im][NTf2] cyclohexene +356.534 323.15 sixth power of the distance between the atoms, I ∝ 1/r.6 In the
[C1C2Im][NTf2] cyclohexane +394.034 323.15 liquid state, this relation is possible if the intermolecular
association is tight enough to turn the intermolecular relaxation
and were found to be 0.857 kJ mol-1 for CYD-[C1C4Im][NTf2] into “intramolecular” within the ion pair or ion-molecule
and 1.629 kJ mol-1 for CYD-[C1C1C4Im][NTf2]. association.41 Highly structured, bulk ionic liquids seem to fulfill
these requirements, thus allowing the use of the intermolecular
E
ROESY to derive lower limits for interionic distances. Conse-
HCYD (kJ/mol) ) a + bxCYD (2) quently, the intensity of the integrals (ICYD-IL) could be
considered as roughly inversely proportional to the intermo-
By integrating eq 1 and taking into account eq 2, we lecular distances (Figure S-4 and S-5, Supporting Information).
E
calculated the excess molar enthalpy of mixing ∆Hmix by Molecular mechanics calculations have been performed using
the SYBYL software with the TRIPOS force field developed
nCYD by Clark et al.44 on isolated pairs of CYD and imidazolium
E
∆Hmix (kJ/mol) ) ∆Hmix ) ∫ 0
E
HCYD dnCYD /(nCYD + nIL) cations. Intermolecular distances were fixed using results from
) (a + b)xCYD + b(1 - xCYD)ln(1 - xCYD) NMR ROESY experiments and the energy of both systems,
(3) CYD-[C1C4Im] and CYD-[C1C1C4Im], were minimized. The
average distances between molecules of CYD and the imida-
From Figure 6, it can be seen that the excess molar enthalpies zolium cations were determined from the geometry at the
of mixing for the binary mixtures of CYD and [C1C4Im][NTf2] potential energy minimum. CYD is mainly located near the butyl
and [C1C1C4Im][NTf2] are positive over the studied range of chain of [C1C4Im][NTf2], the π bonds being located closer to
compositions. The values of excess molar enthalpy of mixing the imidazolium cation, a configuration similar to that previously
of several aromatic and nonaromatic solutes in ILs together with observed for toluene (Figure 7).9
our results are presented in Table 1. To the best of our Access to the microscopic structure of the mixtures in the
knowledge the energetics of solvation of organic solutes in condensed liquid phase is possible using molecular dynamics
[C1C1C4Im][NTf2] had never been studied; therefore, we could simulation with all atoms explicitly present and periodic
establish comparisons only for 3-alkyl-1-methylimidazolium boundary conditions to represent a vitually infinite system.
bis(trifluoromethylsulfonyl)imide, [C1CnIm][NTf2]. Negative Condensed-phase simulations take into account all the two-body
E interactions from the environment of each molecule or ion. The
values of ∆Hmix for benzene and toluene in [C1C4Im][NTf2]
indicate more favorable interactions between aromatic systems molecular simulation details are given in the Experimental
and imidazolium ILs than for methylcyclohexane, for which Section. In Figure 8 are plotted the site-site radial distribution
the enthalpy of mixing is positive. A similar effect was observed functionssthe probability of finding pairs of atoms at a given
in [C1C2Im][NTf2], where the aromatic solutes have more distance, compared to the averagesbetween the hydrogens on
favorable interactions leading to negative enthalpies of mixing Cβ of CYD, Hβ, and selected atoms of the [C1C4Im] and
and higher solubilities. Cyclohexene, due to the presence of a [C1C1C4Im] cations at R ) 0.5 (atoms are labeled as indicated
double bond, also has lower enthalpy of mixing than cyclohex- in Scheme 1). In both cases, there is a higher probability (a
NTf2]. The strong hydrogen bond between C2-H and the anion
in [C1C4Im][NTf2] prevents such an interaction with CYD. This
observation is consistent with the distances between the IL
cations and CYD obtained from ROESY experiments and
molecular mechanics calculations on isolated pairs, as seen in
Figure 7.
Detailed structural features are much better perceived in
3-dimensional spatial distribution functions. In Figure 10 is
represented the distribution of ions around a CYD molecule.
In blue is plotted the iso-surface corresponding to a local density
of twice the average density of C2 carbon atoms of the
imidazolium cations. Cation headgroups (the blue regions) are
located above and below the CYD ring, interacting preferentially
with the π-system of CYD. It can be seen that the terminal
Figure 7. Representation of molecular positions in saturated solutions carbons of the alkyl side chain, C9 (the gray regions), surround
of CYD-[C1C4Im][NTf2] and CYD-[C1C1C4Im][NTf2] from ROESY the CYD molecule. Oxygen atoms of the NTf2- anion (plotted
NMR extrapolation. in red) are found in the plane of CYD interacting with the
hydrogen atoms of the double bonds. Similar results have been
previously obtained for toluene in the same ILs.9 This shows
that although in CYD the π-system is smaller than that of a
fully aromatic system, it still determines the structure of the
solvation shell in ILs with cations positioned above and below
the plane of CYD and anion in the plane.
tel-00708600, version 1 - 15 Jun 2012
Figure 11 shows spatial distribution functions around the

[C1C4Im] and the [C1C1C4Im] cations. With both cations, CYD
(the white regions) is preferentially located above and below
the plane of the imidazolium ring at distances greater than those
of the closest cation-anion pairs. In red is plotted the iso-surface
corresponding to the local density of 4 times the average density
of the oxygen atoms from NTf2- anions. As can be seen, for
[C1C4Im][NTf2] the probability of finding the oxygen of NTf2-
near the C2-H of the imidazolium cation is higher than the
carbon of CYD, indicating a strong H-bond. The situation is
completely different for [C1C1C4Im][NTf2], where the prob-
ability of finding the carbon of CYD near the C2 of the cation
is higher than that of the oxygen atoms of NTf2-. As already
found in the case of solvation of toluene,9 interactions of the
[C1C1C4Im] cation with the anion are mainly through H4, H5
and also the nitrogen atoms, N1 and N3, whereas in [C1C4Im]
cation-anion interactions are mainly through C2-H bonds.
Mass Transport in Reaction Media. To establish whether
the difference in rate of catalytic hydrogenation of CYD can
be attributed to the specific interactions or only to differences
in thermophysical propreties of the reaction media, which affect
the mobility of molecules, the density and viscosity of the
Figure 8. Radial distribution functions between hydrogen on Cβ of mixtures of [C1C4Im][NTf2]-CYD and [C1C1C4Im][NTf2]-CYD
CYD, Hβ, and selected sites in the [C1C4Im] cation (top) and at R ) 0.5 were measured at 298.15 K and atmospheric pressure
[C1C1C4Im] cation (bottom), for R ) 0.5. Atoms are labeled as indicated (Table 2 and Figure S-7 in Supporting Information). The
in Scheme 1. additional methyl group on the imidazolium carbon C2 in
[C1C1C4Im][NTf2] naturally lowers both the mass and molar
stronger association) of finding all hydrogen atoms of CYD near density of the liquid in comparison with [C1C4Im][NTf2]. On
the side chain rather than in the vicinity of the aromatic nucleus the other hand, the viscosity of pure [C1C1C4Im][NTf2] and also
region of the imidazolium cation. This means that CYD is of its mixture with CYD is roughly twice that of
preferentially solvated in the nonpolar domain of the ILs, as [C1C4Im][NTf2], as reported in Table 2. Diffusion coefficients
already observed for saturated hydrocarbons and for the methyl (D) of CYD in both ILs at R ) 0.5 were determined from
group of toluene. This orientation effect relative to the cation extrapolation of DOSY data (Figure S-6 in Supporting Informa-
is less distinct for CYD than for toluene,9 as expected given tion): 187.5 µm2/s in [C1C4Im][NTf2] against 97 µm2/s in
the weaker cation-π interactions of the former. [C1C1C4Im][NTf2], meaning that diffusion of CYD in
Figure 9 represents the comparison of the radial distribution [C1C4Im][NTf2] is 1.9 times faster than in [C1C1C4Im][NTf2].
functions of the mixtures CYD-[C1C4Im][NTf2] and CYD- Since, according to the Stokes-Einstein relation, the diffusion
[C1C1C4Im][NTf2], again at R ) 0.5, between hydrogen on Cβ coefficient is inversely proportional to the viscosity of the
and CR of CYD and C2 of the imidazolium rings. It can be medium, the ratio of values of D obtained is in agreement with
seen that both these hydrogen atoms are found with a higher the ratio of measured viscosities of both mixtures at R ) 0.5,
probability closer to C2 in [C1C1C4Im][NTf2] than in [C1C4Im which is η(CYD-[C1C1C4Im][NTf2])/η(CYD-[C1C4Im][NTf2])
SCHEME 1: Atom Labeling of CYD, 1-Butyl-3-methylimidazolium, and 1-Butyl-2,3-dimethylimidazolium Cations
) 1.9. The availability of H2 for the hydrogenation reaction is comparable within the same order of magnitude. This is
also dependent on the diffusivity of the gas in both ILs. No commensurate with the expected precision of the molecular
experimental data were found on the diffusivity of hydrogen in simulation results.27 All these results indicate that the difference
tel-00708600, version 1 - 15 Jun 2012
ILs, but it is expected that it will also be inversely proportional in reactivity of both systems at R ) 0.5 can be mainly assigned
to the viscosity of the liquid medium since H2 interacts weakly to the difference in viscosity and therefore in mobility of the
with ILs (its solubility is very low45,46). Molecular simulation molecules, namely, CYD in the exchange reaction and both H2
results for the diffusivity of H2 in [C6C1Im][NTf2] at different and CYD in the hydrogenation reaction.
temperatures have recently been published.47 We have calculated
that the increase of diffusivity of hydrogen and the decrease in 4. Conclusion
viscosity of [C6C1Im][NTf2] at the different temperatures48 are
In this work, we studied the impact of two ionic liquid
solvents on the rates of two reaction steps of the catalytic
hydrogenation of 1,3-cyclohexadiene (CYD) with [Rh(COD)-
(PPh3)2]NTf2: the ligand exchange [Rh(COD)(PPh3)2]NTf2 to
[Rh(CYD)(PPh3)2]NTf2, and the catalytic hydrogenation of
CYD itself (COD ) 1,5-cyclooctadiene). It was found that
Figure 10. Spatial distribution functions around the C2 carbon of CYD

in CYD-[C1C4Im][NTf2] (left) and CYD-[C1C1C4Im][NTf2] (right)
at R ) 0.5. In blue is plotted the iso-surface corresponding to a local
density of twice the average density of the C2 carbon of the imidazolium
cations. In gray is plotted the iso-surface corresponding to a local density
of twice the average density of terminal methyl carbons from the butyl
Figure 9. Comparison of site-site radial distribution functions between side chain, C9. In red is plotted the iso-surface corresponding to a local
chosen atoms in CYD and the cations, in CYD-[C1C4Im][NTf2] (top) density of twice the average density of oxygen atoms from the NTf2-
and CYD-[C1C1C4Im][NTf2] (bottom) for R ) 0.5. Atoms are labeled anion. Oxygen atoms are located in the CYD plane interacting with
as indicated in Scheme 1. hydrogen atoms of double bonds, HR and Hβ.
higher diffusion coefficients in [C1C4Im][NTf2] (187.5 µm2/s) when

compared to those in [C1C1C4Im][NTf2] (97 µm2/s), meaning that
diffusion of CYD in [C1C4Im][NTf2] is 1.9 times faster than in
[C1C1C4Im][NTf2]. Since the diffusion coefficient is inversely
proportional to the viscosity of the medium, the values obtained
are in agreement with the Stokes-Einstein relation, since the
ratio of measured viscosities of both ionic liquids at R ) 0.5
η(CYD-[C1C1C4Im][NTf2])/η(CYD-[C1C4Im][NTf2]) is also
1.9. The diffusion coefficient of gases is also expected to vary
inversely with the viscosity of the medium. These results
indicate that the difference in the rate of both ligand exchange
and hydrogenation of CYD with [Rh(COD)(PPh3)2]NTf2 in
[C1C4Im][NTf2] and [C1C1C4Im][NTf2] can be attributed to the
difference in viscosity of both ionic liquids, hence the mobility
of the molecules in solution.
Acknowledgment. A.P. acknowledges the postdoctoral grant

by the project ANR CALIST and P.C. acknowledges the Ph.D.
grant attributed by the Ministère de l’Enseignement Supérieur
Figure 11. Spatial distribution functions around the C2 carbon of the et de la Recherche, France.
cations in CYD-[C1C4Im][NTf2] (left) and CYD-[C1C1C4Im][NTf2]
(right) at R ) 0.5. Above and below are different views of the same
iso-surfaces. In white is plotted the iso-surface corresponding to a local Supporting Information Available: Determination of the
density of twice the average density of CR of CYD. In red is plotted conversion and the composition of the reaction mixture by
tel-00708600, version 1 - 15 Jun 2012
the iso-surface corresponding to a local density of 4 times the average GC. UV-vis spectra of [Rh(COD)(PPh3)2]NTf2 and
density of oxygen atoms from the NTf2- anion. [Rh(CYD)(PPh3)2]NTf2, ROESY and DOSY NMR pulse se-
quences, 1H NMR shifts and ROESY NMR spectra of the
TABLE 2: Density and Viscosity, at 298.15 K and
mixture of CYD in [C1C4Im][NTf2] and [C1C1C4Im][NTf2]. This
Atmospheric Pressure, of Mixtures of CYD-[C1C4Im][NTf2]
and CYD-[C1C1C4Im][NTf2] at R ) 0.5 material is available free of charge via the Internet at http://
pubs.acs.org.
xIL R F (g cm-3) η (mPa s)
CYD-[C1C4Im][NTf2] References and Notes
1.000 0.000 1.4375 48.45
0.667 0.498 1.3597 24.87 (1) Wasserscheid, P.; Welton, T. Ionic Liquids in Synthesis; Wiley
VCH: Weinheim, Germany, 2008.
CYD-[C1C1C4Im][NTf2] (2) Parvulescu, V. I.; Hardacre, C. Chem. ReV. 2007, 107, 2615.
1.000 0.000 1.4177 105.00 (3) Dyson, P. J.; Zhao, D. Hydrogenation. Multiphase Homogeneous
0.662 0.510 1.3442 47.13 Catalysis; Wiley-VCH: Weinheim, 2005; Vol. 2, pp 494.
(4) Olivier-Bourbigou, H.; Vallee, C. Multiphase Homogeneous Ca-
talysis; Wiley-VCH: Weinheim, 2005; Vol. 2, pp 413-431.
both steps are twice as fast in 1-butyl-3-methylimidazolium (5) Hintermair, U.; Gutel, T.; Slawin, A. M. Z.; Cole-Hamilton, D. J.;
bis(trifluoromethylsulfonyl)imide, [C1C4Im][NTf2], than in 1-bu- Santini, C. C.; Chauvin, Y. J. Organomet. Chem. 2008, 693, 2407.
(6) Dupont, J.; Suarez, P. A. Z. Phys. Chem. Chem. Phys. 2006, 8,
tyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, 2441.
[C1C1C4Im][NTf2]. The rate-determining step in both ionic (7) Dupont, J.; Suarez, P. A. Z.; De Souza, R. F.; Burrow, R. A.;
liquids is the hydrogenation of CYD step. Kintzinger, J.-P. Chem.sEur. J. 2000, 6, 2377.
(8) Lachwa, J.; Bento, I.; Duarte, M. T.; Canongia Lopes, J. N.; Rebelo,
Molecular dynamics simulations and NMR experiments L. P. N. Chem. Commun. 2006, 2445.
indicate that in both ILs, for a molar ratio CYD/IL equal to (9) Gutel, T.; Santini, C. C.; Padua, A. A. H.; Fenet, B.; Chauvin, Y.;
0.5, CYD is solvated preferentially in lipophilic regions (in close Canongia Lopes, J. N.; Bayard, F.; Costa Gomes, M. F.; Pensado, A. S. J.
proximity to the alkyl side chains of the cations) as already Phys. Chem. B 2009, 113, 170.
(10) Mele, A.; Romano, G.; Giannone, M.; Ragg, E.; Fronza, G.; Raos,
observed for saturated hydrocarbons and the methyl group of G.; Marcon, V. Angew. Chem., Int. Ed. 2006, 45, 1123.
toluene. In addition, in [C1C1C4Im][NTf2] the probability of (11) Padua, A. A. H.; Costa Gomes, M. F.; Canongia Lopes, J. N. A.
finding CYD near the C2 of the cation is higher than in Acc. Chem. Res. 2007, 40, 1087.
(12) Triolo, A.; Russina, O.; Bleif, H.-J.; Di Cola, E. J. Phys. Chem. B
[C1C4Im][NTf2], in agreement with the shorter CYD- 2007, 111, 4641.
[C1C1C4Im] distances determined by ROESY NMR. On the (13) Canongia Lopes, J. N.; Padua, A. A. H. J. Phys. Chem. B 2006,
other hand, a higher solubility of CYD in [C1C4Im][NTf2] and 110, 3330.
(14) Canongia Lopes, J. N.; Costa Gomes, M. F.; Padua, A. A. H. J.
smaller positive enthalpies of mixing for the CYD-[C1C4Im]- Phys. Chem. B 2006, 110, 16816.
[NTf2] system in comparison with CYD-[C1C1C4Im][NTf2] (15) Hunt, P. A. J. Phys. Chem. B 2007, 111, 4844.
indicate more favorable interactions between CYD and the (16) Magna, L.; Chauvin, Y.; Niccolai, G. P.; Basset, J.-M. Organo-
[C1C4Im] cation than with the [C1C1C4Im] cation. These metallics 2003, 22, 4418.
(17) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 4450.
thermodynamic factors concur with the differences in catalytic (18) Blesic, M.; Canongia Lopes, J. N.; Padua, A. A. H.; Shimizu, K.;
activity, although they cannot fully explain the differences Costa Gomes, M. F.; Rebelo, L. P. N. J. Phys. Chem. B 2009, 113, 7631.
observed. Association between macroscopic thermodynamic (19) Izatt, R. M.; Terry, R. E.; Haymore, B. L.; Hansen, L. D.; Dalley,
N. K.; Avondet, A. G.; Christensen, J. J. J. Am. Chem. Soc. 1976, 98, 7620.
information, thermophysical data, and microscopic structural (20) Liu, Y. F.; Sturtevant, J. M. Protein Sci. 1995, 4, 2559.
information is necessary to fully explain the differences in (21) Briggner, L. E.; Wadso, I. J. Biochem. Biophys. Methods 1991,
reactivity found in both IL media. 22, 101–118.
Pure [C1C1C4Im][NTf2] has a higher viscosity than pure (22) Cutting, B.; Ghose, R.; Bodenhausen, G. J. Magn. Reson. 1999,
138, 326.
[C1C4Im][NTf2], and the same relative values are observed in (23) Canongia Lopes, J. N.; Deschamps, J.; Padua, A. A. H. J. Phys.
the mixtures with CYD. These differences in viscosity induce Chem. B 2004, 108, 2038.
(24) Canongia Lopes, J. N.; Padua, A. A. H. J. Phys. Chem. B 2004, (37) Natori, I.; Imaizumi, K.; Yamagishi, H.; Kazunori, M. J. Polym.
108, 16893. Sci., Part B 1998, 36, 1657.
(25) Canongia Lopes, J. N.; Shimizu, K.; Padua, A. A. H.; Umebayashi, (38) Domanska, U.; Pobudkowska, A.; Eckert, F. Green Chem. 2006,
Y.; Fukuda, S.; Fujii, K.; Ishiguro, S. I. J. Phys. Chem. B 2008, 112, 9449. 8, 268.
(26) Jorgensen, W. L.; Maxwell, D. S.; Tirado-Rives, J. J. Am. Chem. (39) Lachwa, J.; Bento, I.; Duarte, M. T.; Canongia Lopes, J. N.; Rebelo,
Soc. 1996, 118, 11225. L. P. N. Chem. Commun. 2006, 2445.
(27) Maginn, E. J. Acc. Chem. Res. 2007, 40, 1200. (40) Letcher, T. M.; Marsicano, F. J. Chem. Thermodyn. 1974, 6, 509.
(41) Marczak, W.; Verevkin, S. P.; Heintz, A. J. Solution Chem. 2003,
(28) Smith, W.; Forester, T. R.; Todorov, I. T.; The DL_POLY molecular 32, 519.
simulation package, 2.20 ed.; T. D. P. m. s., Ed.; STFC Daresbury (42) Nebig, S.; Bolts, R.; Gmehling, J. Fluid Phase Equilib. 2007, 258,
Laboratorys, Warrington, U.K., 2007. 168.
(29) Chauvin, Y.; Mussmann, L.; Olivier, H. Angew. Chem., Int. Ed. (43) Frezzato, D.; Rastrelli, F.; Bagno, A. J. Phys. Chem.B 2006, 110,
1996, 34, 2698. 5676.
(30) Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 2134. (44) Clark, M.; Cramer, R. D., III; Van Opdenbosch, N. J. Comput.
(31) Costa Gomes, M. F. Unpublished results. Chem. 1989, 10, 982–1012. Sybil program version 7.0, Tripos Inc., 1699
(32) Camper, D.; Becker, C.; Koval, C.; Noble, R. Ind. Eng. Chem. Res. South Hanley Rd., St. Louis, MO 63144, U.S.A.
2006, 45, 445. (45) Jacquemin, J.; Costa Gomes, M. F.; Husson, P.; Majer, V. J. Chem.
(33) Cui, Y.; Biondi, I.; Chaubey, M.; Yang, X.; Fei, Z.; Scopelliti, R.; Thermodyn. 2006, 38, 490. Jacquemin, J.; Husson, P.; Majer, V.; Costa
Hartinger, C. G.; Li, Y.; Chiappe, C.; Dyson, P. J. Phys. Chem. Chem. Gomes, M. F. Fluid Phase Equilib. 2006, 240, 87.
Phys. 2010, 12, 1834. (46) Costa Gomes, M. F. J. Chem. Eng. Data 2007, 52, 472.
(34) Domañska, U.; Żołek-Tryznowska, Z.; Królikowski, M. J. Chem. (47) Shi, W.; Sorescu, D. C.; Luebke, D. R.; Keller, M. J.; Wickra-
Eng. Data 2007, 52, 1872. manyake, S. J. Phys. Chem. B 2010, 114, 6431.
(48) Marsh, K. N.; Brennecke, J. F.; Chirico, R. D.; Frenkel, M.; Heintz,
(35) Kato, R.; Krummen, M.; Gmehling, J. Fluid Phase Equilib. 2004, A.; Magee, J. W.; Peters, C. J.; Rebelo, L. P. N.; Seddon, K. R. Pure Appl.
224, 47. Chem. 2009, 81, 781.
(36) Husson, P.; Pison, L.; Jacquemin, J.; Costa Gomes, M. F. Fluid
Phase Equilib. 2010, DOI: 10.1016/j.fluid.2010.02.021. JP102941N
tel-00708600, version 1 - 15 Jun 2012
Journal of Catalysis 275 (2010) 99–107
Contents lists available at ScienceDirect
Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat
Olefin hydrogenation by ruthenium nanoparticles in ionic liquid media: Does

size matter?
Paul S. Campbell a, Catherine C. Santini a,*, François Bayard a, Yves Chauvin a, Vincent Collière b,
Ajda Podgoršek c, Margarida F. Costa Gomes c, Jacinto Sá d
a
Université de Lyon, Institut de Chimie de Lyon, UMR 5265 CNRS-Université de Lyon-ESCPE Lyon, C2P2, Equipe Chimie Organométallique de Surface,
ESCPE 43 Boulevard du 11 Novembre 1918, F-69616 Villeurbanne, France
b
Laboratoire de Chimie de Coordination, UMR CNRS, 205, route de Narbonne, 31077-Toulouse cedex 04, France
c
Laboratoire de Thermodynamique des Solutions et des Polymères, Université Blaise Pascal, Clermont-Ferrand, 24 Avenue des Landais, 63177 Aubière, France
d
CenTACat, School of Chemistry and Chemical Engineering, Queen’s University, Stranmillis Road, Belfast, Northern Ireland BT9 5AG, UK
tel-00708600, version 1 - 15 Jun 2012
a r t i c l e i n f o a b s t r a c t
Article history: Tailor-made and size-controlled ruthenium nanoparticles, RuNPs, of three distinct sizes between 1 and
Received 1 June 2010 3 nm are generated from the decomposition of (g4-1,5-cyclooctadiene)(g6-1,3,5-cyclooctatriene)
Revised 19 July 2010 ruthenium(0) [Ru(COD)(COT)], under H2 in 1-butyl-3-methylimidazolium bis(trifluoromethanesulpho-
Accepted 21 July 2010
nyl)imide, C1C4ImNTf2, by simply varying experimental conditions. Catalytic hydrogenation of 1,3-cyclo-
hexadiene, CYD, and cyclohexene, CYE, in C1C4ImNTf2, has been used as a probe for the relationship
between size and catalytic performance (activity and selectivity) of RuNPs. To allow comparison between
Keywords:
different reactions, all catalytic reaction mixtures were diligently prepared in order that the parameters
Nanoparticles
Ruthenium
such as substrate/catalyst and substrate/ionic liquid ratio, and therefore, viscosity and mass transport
Ionic liquids factors remained constant. It was found that the catalytic activity increases with the NP size, while high
Size effect selectivity is only observed with the smaller NPs. In addition, the studied RuNPs exhibit a high level of
Selective hydrogenation recyclability with neither loss of activity nor significant agglomeration.
Ó 2010 Elsevier Inc. All rights reserved.
1. Introduction preferentially dissolved in polar domains and non-polar

compounds in non-polar ones [15]. The non-polar organometallic
Transition-metal nanoparticles (NPs) of 1–10 nm in size exhibit complex, Ru(COD)(COT), is expected to be concentrated in the
physicochemical properties intermediate to those of the smallest non-polar domains of ILs. Therefore, the phenomenon of crystal
element from which they can be composed and those of the bulk growth is controlled by the local concentration of Ru(COD)(COT)
material [1–3]. In catalysis, the performance (activity and selectiv- and consequently limited to the size of the non-polar domains.
ity) of NPs is often said to be related to their size, as this controls These play the role of nanoreactors in which the size of ruthenium
the number of corner, edge and face atoms available for adsorption nanoparticles generated in situ can be controlled [13,16,17].
and activation of substrates [4–9]. However, the synthesis of nano- Using NPs formed in situ in ILs directly in catalysis offers the
particles (NPs) with a controlled size in the range of 1–10 nm in opportunity to exploit the distinct physicochemical and solvation
order to corroborate this theory is still a challenging issue [10]. properties of these media, resulting in unique activities and selec-
The use of ionic liquids (ILs) in NP synthesis has recently be- tivities [12,18–21].
come a popular route. The major advantage is that stabilising addi- When comparing the catalytic activity of differently sized nano-
tives such as ligands, polymers and supports are not required. Also, particles, it is important to maintain constant all other possible
we can tune the IL moieties and reaction conditions to obtain variables. Indeed, differences in catalytic activity could have a
monodisperse and catalytically active NPs of controlled size physicochemical origin [22,23], resulting from peculiar solvation
[7,11–13]. This is because imidazolium-based ILs exhibit a 3-D phenomena including specific interactions between the IL and
organisation in the liquid state due to an extended hydrogen-bond the substrate (H bonds, cation-p) [24–26], mass transfer factors
network of ionic channels, coexisting with non-polar domains cre- (viscosity, diffusivity) [22,27], and effects attributed to the highly
ated by the grouping of lipophilic alkyl chains. Consequently, ILs structured nature of ILs [14,28,29].
present specific solvation properties [14]. Polar substrates are It has been shown that it is possible to obtain ruthenium nano-
particles, RuNPs, of differing sizes from the decomposition of Ru
* Corresponding author. Fax: +33 472431795. (COD)(COT) in C1C4ImNTf2, by simply varying the experimental
E-mail address: santini@cpe.fr (C.C. Santini). conditions [16]. In this work, we use the catalytic hydrogenation
0021-9517/$ - see front matter Ó 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcat.2010.07.018
100 P.S. Campbell et al. / Journal of Catalysis 275 (2010) 99–107
of 1,3-cyclohexadiene, CYD, and cyclohexene, CYE, as probes for carbon). Binding energies were determined with an accuracy of
the relationship between size and catalytic performance of tailor- ±0.2 eV. The data were analysed using Casa-XPS (v 2.3.13) employ-
made and size-controlled RuNPs, generated in the ionic liquid, all ing a Shirley background subtraction prior to fitting and a peak
other physicochemical variables being constant. shape with a combination of Gaussian and Lorentzian (30%
Lorentzian). High-resolution spectra were acquired in the region
2. Experimental of Ru 3p as the Ru 3d region overlaps with the C 2p region of the
residual ionic liquid.
2.1. Materials and methods
2.5. Preparation of catalytic experiments
All operations were performed in the strict absence of oxygen
and water under a purified argon atmosphere using glovebox (Jac- In Table 1 are collected all data concerning the studied hydroge-
omex or MBraun) or vacuum-line (Schlenk) techniques. The ionic nation reaction. In columns 1–3, size and dispersion values of
liquid, C1C4ImNTf2 [30], and the complex, [Ru(COD)(COT)] [31], (Ru0), (Ru25) and (Ru50) are reported.
were synthesised as reported. The halide content of the ionic liquid Each solution of NP was produced from the decomposition of
was under 200 ppm (E.A.) and water under 5 ppm (limit of Karl 43.0 mmol Lÿ1 solution of Ru(COD)(COT) as described in Section
Fischer titration). Elemental analyses were performed at the CNRS 2.2 and shown in column 4.
Central Analysis Department of Solaize. For each different temperature of decomposition, a different
1-Methylimidazole (>99%) was purchased from Aldrich and dis- size of NP is obtained: at 0 °C, 1.1 nm (Ru0); at 25 °C, 2.3 nm
tilled prior to use. Chlorobutane (>99%, Aldrich) and lithium bis(tri- (Ru25); and at 50 °C, 2.9 nm (Ru50), shown in columns 1 and 2.
fluoromethanesulfonyl)imide (Solvionic) were used without The value of dispersion, D, describing the ratio of surface sites
further purification. Rus to total number of ruthenium atoms, varies with the NP size
and is given for each size of NP in column 3. Using this and the
tel-00708600, version 1 - 15 Jun 2012
known concentration of ruthenium (43.0 mmol Lÿ1), it is possible

2.2. Catalyst synthesis
to calculate for each size of catalyst the concentration of Rus (col-
umn 5). For example, for Ru0 (1.1 nm), we have a dispersion of 82%
A solution of (g4-1,5-cyclooctadiene)(g6-1,3,5-cyclooctatri-
and therefore a Rus concentration of 35.2 mmol Lÿ1.
ene)ruthenium(0) Ru(COD)(COT) (43 mmol Lÿ1) in the ionic liquid
To prepare the catalytic mixtures, we must have the same num-
1-butyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide
ber of catalyst sites. For this reason, we dilute the most concen-
(C1C4ImNTf2) was transferred under argon to a glass autoclave,
trated solutions, i.e. Ru0 and Ru25, to match the least
the temperature of which was controlled with aid of a thermostatic
concentrated, i.e. Ru50, by the addition of the appropriate amount
bath (0, 25, 50 or 75 °C). Once stabilised, the argon atmosphere was
of pure IL.
evacuated and replaced with molecular hydrogen (4 bar) without
Ru50 has a concentration of Rus of 18.5 mmol Lÿ1. A 5-mL sam-
stirring. The yellow solution turned black over time (up to 3 days)
ple of this solution therefore contains 9.52 10ÿ5 mol of Rus.
as RuNPs were generated releasing cyclooctane (COA) as the only
Ru25 has a concentration of Rus of 22.9 mmol Lÿ1. A 3.74-mL
by-product. The resulting solutions were treated under dynamic
sample of this solution is therefore taken, containing
vacuum during a period of 6 h to remove all H2 and cyclooctane.
9.52 10ÿ5 mol of Rus, and then diluted with 1.26 mL of pure IL
The black solutions could then be stored under argon atmosphere
to make a 5-mL solution.
with long-term stability (at least 6 months – no precipitation, coa-
Ru0 has a concentration of Rus of 35.2 mmol Lÿ1. A 2.58-mL
lescence or agglomeration – verified by TEM).
sample of this solution therefore contains 9.52 10ÿ5 mol of Rus
diluted with 2.42 mL of pure IL to make a 5-mL solution (columns
2.3. Determination of particle size by TEM 6–8).
To each of these 5-mL catalyst/IL solutions, weighing 7.0 g (col-
Transmission electron microscopy (TEM) experiments were umn 9), is added 0.78 g of CYD (column 10). This gives catalytic
performed directly in the IL media. A thin film of RuNP solution mixtures with constant substrate/catalyst ratios of 105 (column
in IL was deposited on a carbon film supported by a copper grid. 11) and constant substrate/IL ratios of 0.59 (column 12) ensuring
Conventional TEM micrographs were obtained at the Centre Tech- identical viscosities and a single phase.
nologique des Microstructures, Université Claude Bernard Lyon 1, Using solutions prepared as described, the reaction is carried
Villeurbanne, France, using a Philips 120 CX electron microscope out in parallel in several 0.5-mL batches under 1.2 bars of pure
with acceleration voltage of 120 kV. Size distribution histograms molecular hydrogen, which are stirred and heated with the aid of
were constructed from the measurement of at least 200 different a thermostatic carousel, to ensure identical reaction conditions.
nanoparticles assuming a near spherical shape and random orien-
tation. High-resolution electron micrographs were obtained at the 2.6. Catalytic tests
‘‘TEMSCAN” centre of the Université Paul Sabatier Toulouse 3, Tou-
louse, France, using a JEOL JEM 200CX electron microscope with Catalytic solutions were made as described in Section 2.5 in a
acceleration voltage of 200 kV. glove box and left stirring for 12 h in a closed system to ensure
homogeneity. Aliquots of 0.5 mL were transferred to identical
2.4. XPS Schlenk tubes containing cross-shaped magnetic stirrer bars. The
argon atmosphere was removed, and the solution was degassed
X-ray photoelectron spectroscopy was performed in a Kratos in vacuo whilst cooling in liquid nitrogen (ÿ196 °C). For reactions
Axis Ultra DLD spectrometer, using a monochromated Al Ka X- at 30 °C, six of these Schlenk tubes were placed in a thermostatic
ray with a pass energy of 20 eV and a coaxial charge neutraliser. carousel to ensure identical temperature and stirring conditions.
The base pressure in the analysis chamber was better than After 30 min, when the temperature had stabilised, the Schlenk
5 10ÿ8 Pa. XPS spectra of Ru3p, C1s, Si2p and O1s levels were tubes were opened to 1.2 bars of H2. After t minutes, a Schlenk tube
measured at a normal angle with respect to the plane of the sur- was isolated and opened to air, releasing the H2 atmosphere thus
face. High-resolution spectra were corrected for charging effects quenching the reaction. The solution was entirely dissolved in
by assigning a value of 284.6 eV to the C1s peak (adventitious 10 mL of acetonitrile containing a 1 M concentration of toluene.
P.S. Campbell et al. / Journal of Catalysis 275 (2010) 99–107 101
Table 1
Calculations for the composition of the catalytic systems. Column 1 – name of catalyst, column 2 – average RuNP diameter measured by TEM, column 3 – calculated dispersion,
column 4 – initial Ru(COD)(COT) concentration, column 5 – consequent Rus concentration, column 6 – volume of IL/RuNP solution, column 7 – volume of pure IL added, column 8
– consequent number of moles of Rus in the 5 mL mixture, column 9 – mass of IL, column 10 – mass of substrate, column 11 – substrate/catalyst ratio, column 12 – substrate/IL
ratio.
1 2 3 4 5 6 7 8 9 10 11 12
d D [Ru] (mmol Lÿ1) [Rus] (mmol Lÿ1) Vol. IL–RuNP Vol. IL pure (mL) Rus/10ÿ5 (mol) m (IL/g) m (CYD/g) CYD/Rus CYD/IL
(nm) (%) solution (mL)
Ru0 1.1 82 43.0 35.2 2.42 2.58 9.52 7.0 0.78 105 0.59
Ru25 2.3 53 43.0 22.9 3.74 1.26 9.52 7.0 0.78 105 0.59
Ru50 2.9 43 43.0 18.5 5.00 – 9.52 7.0 0.78 105 0.59
The composition of the mixture was determined by gas-phase CYD may be partially hydrogenated with high selectivity by molec-
chromatography using toluene as the internal standard. ular catalysts due to the reduced miscibility of cyclohexene (CYE)
in the medium [27,32,33]. Full hydrogenation would lead to cyclo-
2.7. Product quantification hexane (CYA), Scheme 1.
The products were quantitatively analysed by gas chromatog- 3.2. Solubility

raphy on a HP-6890 chromatograph equipped with a flame ioni-
sation detector (FID) and a HP-1 (crosslinked methylsiloxane) The solubilities of the substrate and potential products may
column (L: 30 m, int: 0.32 mm, film thickness: 0.25 lm). The play an important role in the activity and/or selectivity of the sys-
injector and detector temperature was 270 °C, and the injection tem. For example, selective hydrogenation of butadiene to butenes
tel-00708600, version 1 - 15 Jun 2012
volume was 1 lL. The programme was as follows: initial temper- has been performed by Dupont’s group in ionic liquids due to the
ature 70 °C for 13.5 min; ramp 40 °C/min to 250 °C, hold 2 min. difference in solubility of the partially hydrogenated product
[34]. The same group has also described the possibility of extract-
ing cyclohexene during benzene hydrogenation using this solubil-
2.8. Density and viscosity
ity difference [35]. For this reason, solubilities of CYD, CYE and CYA
are measured. It is found that the solubility of the hydrogenated
The mixtures of IL and CYD at different compositions were pre-
products (6 ± 1% wt – CYE, 4 ± 1% wt – CYA) is much lower than
pared gravimetrically following the procedure already described
that of CYD (12 ± 2% wt); therefore, the medium may tend to a
[27]. The viscosity of the mixture was measured at 298.15 K
biphasic system during the course of the reaction. As a result, the
(controlled to within ±0.005 K and measured with the accuracy
collection of aliquots from a single batch would render inaccurate
better than ±0.05 K) using a rolling-ball viscometer from Anton
results. Consequently, each point recorded in this work corre-
Paar, model AMVn [27]. The overall uncertainty of the viscosity
sponds to a separate experiment, quenched after time t by opening
is estimated as ±2.0%. The densities of the mixtures, necessary to
the reaction vessel to air, thus releasing the hydrogen and dissolv-
calculate the viscosities, were measured in an Anton Paar vibrating
ing the catalytic system entirely in a 1 M solution of toluene in ace-
tube densimeter model 512 P, at 298.15 K (measured by a cali-
tonitrile for gas-phase chromatography.
brated PRT with an accuracy of ±0.02 K). The overall uncertainty
of the density is estimated as ±0.01%.
3.3. Viscosity
2.9. Solubility Thermophysical properties of the reaction medium such as den-

sity and viscosity may also influence the catalytic performance. We
To measure the solubility, 1 mL of the substrate was stirred have recently demonstrated that reaction kinetics in IL media are
with the ionic liquid in a closed system at 298.15 K for 12 h and highly dependent on the mobility of molecules [27]. Consequently,
then left to settle for a further 2 h. A 0.1-mL sample of the ionic identical concentrations of substrate must be used in each case in
liquid phase was weighed, and its composition was determined order to maintain constant viscosity and eliminate effects due to
by GC using the procedure described in Section 2.6. Tests were mass transport. Furthermore, knowledge of the viscosity is very
repeated four times for each substrate to guarantee reproducibility. important from engineering point of view as it plays a major role
in stirring, mixing and pumping processes. The densities and vis-
3. Results and discussion cosities of the pure C1C4ImNTf2 and those of the mixtures with
CYD were measured at different molar ratio CYD/IL (R) at 25 °C
3.1. Choice of substrate and atmospheric pressure. The results are presented in Table 2.
As can be seen, the viscosity of the mixtures of CYD in IL varies
The substrate investigated is the conjugated diene, 1,3-cyclo- greatly with the concentration of CYD. From the Stokes–Einstein
hexadiene (CYD). It has been shown that in ionic liquid media,
Table 2
Density, q, and viscosity, g, of CYD–IL mixtures of different compositions. xIL = molar
fraction of IL, R = molar ratio CYD/IL.
H2 R xIL q (g cmÿ3) g (m Pa s)
+ 0.000 1.000 1.4376 ± 0.0001 48.5 ± 0.4
0.100 0.909 1.4202 ± 0.0001 44 ± 1
0.200 0.833 1.3999 ± 0.0001 37.0 ± 0.4
0.300 0.769 1.3874 ± 0.0003 33.3 ± 0.3
CYD CYE CYA 0.397 0.716 1.3718 ± 0.0001 31.0 ± 0.3
0.498 0.667 1.3597 ± 0.0001 24.8 ± 0.3
Scheme 1. 1,3-Cyclohexadiene and its hydrogenation products.
relation, the diffusion coefficient, D, which reflects to the mobility 160

of molecules, varies inversely with g,
140 T = 0 °C
kT
D¼ ð1Þ T = 25 °C
6pgr s 120
T = 50 °C
100 T = 75 °C
Frequency
3.4. Catalyst characterisation
80
It has been previously demonstrated that the size of RuNPs
60
generated from the decomposition of [Ru(COD)(COT)] under H2
[36], may be governed by the degree of self-organisation of the 40
imidazolium-based ionic liquid in which they are formed: the
more structured the ionic liquid, the smaller the size [16]. Follow- 20
ing previously described methods, RuNPs are synthesised at 0 °C,
0
25 °C, 50 °C and 75 °C in an attempt to obtain a selection of mono-
1 2 3 4 5
disperse sizes of RuNP in the same IL.
Size/ nm
3.4.1. TEM Fig. 2. Comparative size distribution histograms for RuNPs prepared in C1C4Im NTf2
Analysis of the suspensions obtained by transition electron at different temperatures.
microscopy allows the determination of the sizes generated:
1.1 ± 0.2 nm, 2.3 ± 0.3 nm, 2.9 ± 0.4 nm and 3.1 ± 0.7 nm, for RuNPs interplanar distances match with the hcp crystalline phase of Ru
generated at 0 °C (Ru0), 25 °C (Ru25), 50 °C (Ru50) and 75 °C (Ru75), (see Supplementary information). For Ru0, only a larger NP of
2 nm is observed by HREM, probably due to the difficulty in
tel-00708600, version 1 - 15 Jun 2012
respectively, Fig. 1. As can be seen from the TEM image of Ru75 and
the consequent size distribution histogram Fig. 2, the size of these observing the smallest NPs with limited contrast although may
NPs does not vary significantly compared to those of Ru50 although be indicative of a lower degree of crystallinity in very small RuNPs,
a poorer size control (wider distribution) is apparent. For this rea- as already observed by reverse Monte Carlo simulations.[37].
son, these NPs are not used in catalytic tests. High-resolution elec-
tron microscopy reveals the crystalline nature of the RuNPs formed 3.4.2. XPS
through elucidation of the crystal planes. The Fourier transform In order to establish the oxidation state of the RuNPs, X-ray
images of the HREM have been exploited and indicate that the photoelectron spectroscopy (XPS) is performed. Due to the weak
Fig. 1. Transition electron micrograph of RuNPs and high-resolution electron micrograph examples showing crystallinity for Ru0 (top left), Ru25 (top right), Ru50 (bottom left)
and Ru75 (bottom right).
Ru 3p1/2 Ru 3p3/2 Ru 3p1/2 Ru 3p3/2

Ru 3p3/2
Ru 3p1/2
490 480 470 460 450 490 480 470 460 450 490 480 470 460 450
Binding Energy / eV Binding Energy / eV Binding Energy / eV
Fig. 3. XPS spectra of the Ru 3p region after NP filtration onto SiO2, experimental data and fitted peaks. Left Ru0, middle Ru25 and right Ru50.
100%
concentration of the solution and the penetration limit of the
90%
X-rays in the solution (maximum depth of 10 nm), no peaks corre-
sponding to Ru binding energies are observed when the analyses 80%
are carried out directly on the RuNP/IL solutions. Samples are 70%
Dispersion
therefore prepared by filtering the RuNPs onto silica under inert 60%
atmosphere and eliminating as much IL as possible. The resulting
tel-00708600, version 1 - 15 Jun 2012
50%
spectra of the Ru 3p region are depicted in Fig. 3. It is clear that
in each case, fine peaks are observed, indicating the presence of 40%
only one Ru species. The low 3p3/2 binding energy observed in each 30%
case, 460.3 eV, and doublet separation of 22.2 eV correspond clo- 20%
sely to metallic zero-valent ruthenium, often reported with a
10%
3p3/2 binding energy of around 461 eV [38]. The small difference
may be attributed to the presence of small crystallites, which tend 0%
0 0.5 1 1.5 2 2.5 3 3.5
to exhibit lower binding energies than bulk metal. Indeed, as re-
cently shown for AuNPs [39], the d band narrows with decreasing Diameter / nm
particle size and shifts towards the Fermi level. Fig. 4. Curve of dispersion D against mean diameter of crystalline hcp RuNPs.
3.5. Rus concentration

in several 0.5-mL batches under 1.2 bars of pure molecular hydro-
Maintaining constant the initial ratio of substrate to catalyst is gen, which are stirred and heated with the aid of a thermostatic
imperative. In NP catalysis, as in heterogeneous catalysis, only the carousel, to ensure identical reaction conditions.
atoms at the surface (Rus) take part in reaction. The dispersion (D)
presents the ratio between surface atoms, Rus, and the total num-
3.7. Catalytic activity
ber of atoms, RuT, (D = Rus/RuT) and varies with the size of the NPs,
smaller particles of course having a larger percentage of surface
It can be seen in Table 3 (Experiments 1–3) that the largest NPs
atoms. The different dispersion values must therefore be taken into
(2.9 nm) are the most active in the hydrogenation of CYD. In a sim-
account for each size of nanoparticle formed.
ilar fashion, the three sizes of RuNP are tested in the catalytic
Ruthenium is known to exhibit a hexagonal close-packed crys-
hydrogenation of cyclohexene (CYE) to cyclohexane (CYA) to
tal structure, with the following lattice parameters: a: 270.59 pm,
establish whether a difference in activity is also apparent in the
b: 270.59 pm, c: 428.15 pm, a: 90°, b: 90°, c: 120° [40]. Using these
case of a monoene. The results tabulated in Table 4 show that no
parameters, SYBYL software can be applied to extrapolate the lat-
substantial difference in activity is observed unlike the case of
tice until the measured diameters in order to model the structure
the conjugated diene CYD.
of the different size NPs, assuming crystallinity. It is seen that crys-
In the case of in the catalytic hydrogenation of cyclohexene
talline hexagonal close-packed RuNPs would adopt a truncated
(CYE) to cyclohexane (CYA), the TOF value for Ru0 is comparable
hexagonal bipyramid form, with two symmetric hexagonal faces
to that reported by Roucoux’s group with RuNPs (2.5 nm,
(0 0 0 1) and 12 irregular and uneven trapezoid faces (1 0 (ÿ1) 1)
TOF = 34) in water in the presence of cyclodextrins [42], although
[41]. From these findings, a curve of D with respect to diameter
clearly here the experimental conditions are entirely different.
can be plotted and then used to estimate D for each size of nano-
According to literature results, the catalytic activity of NPs
particle, Fig. 4.
depends on their size and generally reaches a maximum for those
of around 3 nm [43,44]. Here, only a size effect on activity was
3.6. Catalysis mixture preparation observed for the case of CYD. The fact that the hydrogenation of
CYD is faster with larger NPs can be related to two factors:
In Table 2 (Section 2.6) are collected all data concerning the
studied hydrogenation reaction. The experimental conditions are (1) Larger NPs present the appropriate number of neighbouring
established to ensure identical concentrations of Rus (column 8) surface sites to facilitate the p-bond activation of the conju-
and substrate (columns 9 and 10), permitting as a result both a gated system [45].
constant substrate/catalyst ratio (column 11) and a constant sub- (2) Through this p-bonding activation similar to benzene, 1,3-
strate/IL ratio (column 12) hence constant viscosity. Using solu- cyclohexadiene would lose part of its resonance energy
tions prepared as described, the reaction is carried out in parallel and react more readily [41].
Table 3
Conversion, selectivity, turnover number and turnover frequency for the hydrogenation of CYD at 30 °C. Experiments 1–3 using 1.2 bar H2. Experiments 4 and 5 using 4 bar H2.
Experiment number Catalyst (nm) Pressure H2 (bar) Conversion at 90 min (%) Selectivity CYE (%) TON TOF (hÿ1) Size after catalysis (nm)
1 Ru0 (1.1) 1.2 66 ± 5 97 70 ± 5 46 ± 3 1.3 ± 0.4
2 Ru25 (2.3) 1.2 75 ± 5 86 79 ± 5 53 ± 3 2.1 ± 0.5
3 Ru50 (2.9) 1.2 83 ± 5 80 87 ± 5 58 ± 3 2.7 ± 0.5
4 Ru0 (1.1) 4.0 57 ± 5 92 59 ± 5 40 ± 3 –
5 Ru50 (2.9) 4.0 73 ± 5 80 77 ± 5 51 ± 3 –
Table 4 the hydrogenation of 1,3-cyclohexadiene on metallic surfaces

Conversion, turnover number and turnover frequency for the hydrogenation of CYE at [46,47], and thus, rapid consecutive hydrogenation of both double
30 °C under 1.2 bar H2.
bonds leading to the fully hydrogenated CYA may be envisaged. In
Experiment Catalyst Conversion at 90 min TON TOF Fig. 6 are represented simplified SYBYL models of CYD molecules
number (nm) (%) (hÿ1) coordinating to the surface of perfectly crystalline RuNPs of calcu-
6 Ru0 (1.1) 61 ± 5 64 ± 5 43 ± 3 lated average diameter 1.3 nm and 2.8 nm. This illustrates nicely
7 Ru25 (2.3) 64 ± 5 67 ± 5 45 ± 3 the greater facility of planar coordination to faces of the larger
8 Ru50 (2.9) 67 ± 5 70 ± 5 47 ± 3
NPs and could explain the lower selectivity of the larger RuNPs de-
spite identical reaction conditions. Likewise, in the hydrogenation
The coordination of monoenes such as CYE does not necessitate of 1,3-butadiene or 1-hexyne, the selectivity of small NPs towards
large surfaces, explaining the less pronounced size effect in this 1-butene or 1-hexene versus butane or hexane is still higher than
case. that of larger NPs [45–48]. In this work, in the hydrogenation of
tel-00708600, version 1 - 15 Jun 2012
CYD, the selectivity in CYE versus CYA drops from 97% to 80% when
the RuNP size increases from 1.1 to 2.9 nm.
3.8. Catalytic selectivity Our hypothesis is based on idealised particle shape, which is not
likely to exist in reality. Nonetheless, it is widely accepted that
In the hydrogenation of CYD, CYE is obtained as the major prod- large NPs are more likely to present larger open facets where pla-
uct. Interestingly, the selectivity for CYE diminishes with increas- nar p-coordination of diene substrates can occur, whereas small
ing NP size. Indeed, for Ru0, selectivity for CYE is 100% at low NPs are often reported to be amorphous, therefore presenting no
conversion and only slightly diminishes at high conversion (97%). open facets, making this planar coordination even less likely [41].
In contrast, for Ru50, the hydrogenation is unselective even at In studies of CO hydrogenation on RhNPs, the difference in reac-
low conversion, Fig. 5. tivity with size was related to the increasing probability of finding
Assuming highly crystalline particles with hcp structure, a par- step sites with increasing NP size [49–51]. However, for RuNPs of
ticle of diameter 1.1 nm would have the vast majority of catalytic less than 3 nm, as reported here, calculations have shown that such
surface atoms occupying vertex or edge positions. Such vertex step sites are not likely to exist [52].
ruthenium atoms Ruv, which under H2 atmosphere are ligated by The highly selective hydrogenation of 1,3-cyclohexadiene to
hydrides, may coordinate one C@C double bond of CYD. The prod- cyclohexene has also been performed with PdNPs in organic and
uct of the subsequent hydrogenation is CYE, which must undergo a IL media [33,53,54]. The high selectivity results from the intrinsic
second coordination to give the fully hydrogenated CYA. Similarly, properties of Pd metal and its small NP size [55].
for a larger particle of average diameter 2.9 nm assuming high
crystallinity and an hcp structure, it is evident that most of the cat- 3.9. Hydrogen effect
alytically active surface ruthenium atoms are found in facial posi-
tions, Ruf. Indeed, here, such crystallinity has already been According to the literature, the hydrogenation of olefins in ILs is
observed by HREM, Fig. 1. Ruf may hydrogenate the olefin using often biphasic in its nature [56–59], due to the poor solubility of
the mechanism previously discussed, but due to the planar hydrogen and olefins in these media [60–63]. Therefore, the diffu-
arrangement of Ruf, another mechanism may be envisaged involv- sion process of the substrate or H2 may limit the rate of
ing the double coordination of the diene, as generally found during hydrogenation.
To find out whether H2 is in fact a rate-limiting reagent, exper-
iments varying the H2 pressure are performed. Increasing H2 pres-
sure to 4 bars in the case of Ru0 and Ru50 is seen to affect neither
the activity nor selectivity in a substantial manner, Table 3, Exper-
iments 4 and 5. This is similar to results reported by Dupont’s
group who observed that the reaction rate does not depend on
the H2 pressures in C1C4ImBF4 [64].
In parallel, it is generally reported that a higher H2 concentra-
tion should influence the activity of the large rather than small par-
ticles, as the H2 storage capacity is related to the particle volume;
therefore, large particles may experience an increase in the avail-
ability of subsurface hydrogen [44].
In reality, little difference in activity is observed in either case.
This proves that the rate is not dictated by the availability and
adsorption of H2, in agreement with observations of labile surface
hydrides on the NP surface [17], but by the mobility and absorption
of the substrate [26]. Indeed, it is highly likely that the surface of
Fig. 5. Selectivity for cyclohexene as a function of conversion for the three different the NPs is already saturated with adsorbed H2 at the temperature
sizes of RuNPs. of the reaction [17].
tel-00708600, version 1 - 15 Jun 2012
Fig. 6. SYBYL representations of CYD coordinated to the face of highly crystalline RuNPs of mean diameter 1.3 nm (left) and 2.8 nm (right).
Fig. 7. Transition electron micrographs of RuNPs after CYD hydrogenation for Ru0 (left), Ru25 (middle) and Ru50 (right).
Table 5
Recycling of the catalyst Ru0. Conversion, selectivity, turnover number and turnover frequency for the hydrogenation of CYD at 30 °C under 1.2 bar H2. Products removed under
vacuum after each run and analysed by GC.
Experiment number Cycle Conversion at 90 min (%) Selectivity CYE (%) TON TOF (hÿ1) Size after catalysis (nm)
1 1st 66 97 70 46 1.3 ± 0.4
9 2nd 73 95 76 51 –
10 3rd 69 94 73 49 –
11 4th 68 89 71 47 –
12 5th 64 86 67 45 –
13 6th 65 86 68 45 1.8 ± 0.5
3.10. Recycling the most selective catalyst, Ru0, recycling experiments are per-
formed, by extracting in vacuo and quantifying the volatiles after
TEM images of the reaction medium after hydrogenation, Fig. 7, each 90-min run. More CYD is then added for hydrogenation. From
show that the average size measured (Table 3) does not differ the results, Table 5 and Fig. 8, it can be seen that both the activity
greatly from the original size, in accordance with the stability of and selectivity remain high after five recycles, diminishing only
RuNPs in ILs under molecular hydrogen [17]; however, the size dis- slightly with each run. This small decrease of course is attributable
tribution is larger, probably as an effect of stirring [65]. to the gradual coalescence of the NPs, leading to a diminution in
The apparent resistance to coalescence of the NPs means that the number of active surface sites and larger, less selective NPs.
they may be tested for their recyclability. Consequently, using Indeed, TEM images obtained of the NPs after all recycling
55 100 References
Selectivity for cyclohexene / %

TOF
Selectivity for cyclohexene [1] M. Valden, X. Lai, D.W. Goodman, Science 281 (1998) 1647.
50
90 [2] A.T. Bell, Science 299 (2003) 1688–1691.
[3] G. Schmid, Nanoparticles: From Theory to Application, Wiley-VCH, Weinheim,
45 2004.
[4] K. Lee, M. Kim, H. Kim, J. Mater. Chem. 20 (2010) 3791–3798.
TOF / h-1
80
[5] A.Z. Moshfegh, J. Phys. D: Appl. Phys. 42 (2009) 233001. 233032.
40 [6] G.A. Somorjai, J.Y. Park, Top. Catal. 49 (2008) 126–135.
[7] H. Boennemann, K.S. Nagabhushana, in: B. Corain, G. Schmid, N. Toshima
70 (Eds.), Metal Nanoclusters in Catalysis and Materials Science: The Issue of Size
35 Control, Elsevier B.V., Amsterdam, pp. 21–48.
[8] H. Bönnemann, K.S. Nagabhushana, R.M. Richards, in: D. Astruc (Ed.),
60 Nanoparticles and Catalysis, Wiley-VCH, Weinheim, 2008, pp. 49–92.
30
[9] H. Tada, T. Kiyonaga, S. Naya, Chem. Soc. Rev. 38 (2009) 1849.
[10] D. Astruc, Nanoparticles and Catalysis, Wiley-VCH, Weinheim, 2008.
25 50 [11] J. Dupont, J.D. Scholten, Chem. Soc. Rev. 39 (2010) 1780–1804.
1 2 3 4 5 6 [12] J. Dupont, Nanoparticles and Catalysis, Wiley-VCH, Weinheim.
[13] T. Gutel, C.C. Santini, K. Philippot, A. Padua, K. Pelzer, B. Chaudret, Y. Chauvin,
Cycle J.-M. Basset, J. Mater. Chem. 19 (2009) 3624–3631.
[14] A.A.H. Padua, M.F. Costa Gomes, J.N.A. Canongia Lopes, Acc. Chem. Res. 40
Fig. 8. Evolution of TOF and selectivity with catalyst recycling. (2007) 1087–1096.
[15] J.N. Canongia Lopes, M.F. Costa Gomes, A.A.H. Padua, J. Phys. Chem. B 110
(2006) 16816–16818.
experiments showed that the NPs undergo coalescence to attain an
[16] T. Gutel, J. Garcia-Anton, K. Pelzer, K. Philippot, C.C. Santini, Y. Chauvin, B.
average diameter of 1.8 ± 0.5 nm, approaching the size of Ru25 and Chaudret, J.-M. Basset, J. Mater. Chem. 17 (2007) 3290–3292.
of course presenting a similar selectivity. [17] P.S. Campbell, C.C. Santini, D. Bouchu, B. Fenet, K. Philippot, B. Chaudret, A.A.H.
Padua, Y. Chauvin, Phys. Chem. Chem. Phys. 12 (2010) 4217–4223.
[18] C. Vollmer, E. Redel, K. Abu-Shandi, R. Thomann, H. Manyar, C. Hardacre, C.
tel-00708600, version 1 - 15 Jun 2012
4. Conclusion Janiak, Chem. Eur. J. 16 (2010) 3849–3858. S3849/3841-S3849/3834.

[19] E. Redel, J. Kraemer, R. Thomann, C. Janiak, J. Organometal. Chem. 694 (2009)
1069–1075.
In this work, the catalytic hydrogenation of 1,3-cyclohexadiene, [20] M.H.G. Prechtl, J.D. Scholten, J. Dupont, J. Mol. Catal. A 313 (2009) 74–78.
CYD, and cyclohexene, CYE, in C1C4ImNTf2, was used as a probe for [21] B. Leger, A. Denicourt-Nowicki, H. Olivier-Bourbigou, A. Roucoux, Inorg. Chem.
47 (2008) 9090–9096.
the relationship between size and catalytic performance of RuNPs.
[22] P. Wasserscheid, T. Welton, Ionic Liquids in Synthesis, Wiley-VCH, Weinheim,
Firstly, tailor-made, size-controlled and zero-valent RuNPs 2008.
(1–3 nm) were generated from the decomposition of [Ru(COD) [23] H. Olivier-Bourbigou, C. Vallee, Multiphase Homogeneous Catalysis, Wiley-
(COT)] under H2 in C1C4ImNTf2, by varying the experimental condi- VCH, Weinheim, pp. 413–431.
[24] J. Dupont, P.A.Z. Suarez, R.F. De Souza, R.A. Burrow, J.-P. Kintzinger, Chem. Eur.
tions. RuNPs were fully characterised in situ by TEM and HREM to J. 6 (2000) 2377–2381.
determine their sizes and demonstrate their degree of crystallinity [25] J. Lachwa, I. Bento, M.T. Duarte, J.N.C. Lopes, L.P.N. Rebelo, Chem. Commun.
and ex situ by XPS to verify their zero oxidation state. (2006) 2445–2447.
[26] T. Gutel, C.C. Santini, A.A.H. Padua, B. Fenet, Y. Chauvin, J.N. Canongia Lopes, F.
Secondly, all catalytic reaction compositions were carefully cal- Bayard, M.F. Costa Gomes, A.S. Pensado, J. Phys. Chem. B 113 (2009) 170–177.
culated in order that all parameters except particle size were main- [27] P.S. Campbell, A. Podgorsek, T. Gutel, C.C. Santini, A.A.H. Padua, M.F. Costa
tained constant, i.e. Rus concentration, CYD/Rus ratio and CYD/IL Gomes, F. Bayard, B. Fenet, Y. Chauvin, J. Phys. Chem. B 114 (2010) 8156–8165.
[28] A. Mele, G. Romano, M. Giannone, E. Ragg, G. Fronza, G. Raos, V. Marcon,
ratio, the latter governing solvation phenomena and mass transfer Angew. Chem. Int. Ed. 45 (2006) 1123–1126.
factors (viscosity and diffusivity). It was found that for catalytic [29] A. Triolo, O. Russina, H.-J. Bleif, E. Di Cola, J. Phys. Chem. B 111 (2007) 4641–4644.
hydrogenations of CYD and CYE, the activity of catalyst increases [30] L. Magna, Y. Chauvin, G.P. Niccolai, J.-M. Basset, Organometallics 22 (2003)
4418–4425.
with the NP size in agreement with the literature results on heter-
[31] P. Pertici, G. Vitulli, Inorg. Synth. 22 (1983) 176–181.
ogeneous catalysts. In contrast to activity, in the hydrogenation of [32] Y. Chauvin, S. Einloft, B.H. Olivier, Ind. Eng. Chem. Res. 34 (1995) 1149–1155.
CYD, the selectivity for CYE versus CYA drops from 97% to 80% [33] J. Huang, T. Jiang, B. Han, H. Gao, Y. Chang, G. Zhao, W. Wu, Chem. Commun.
(2003) 1654–1655.
when the RuNP size increases from 1.1 to 2.9 nm.
[34] A.P. Umpierre, G. Machado, G.H. Fecher, J. Morais, J. Dupont, Adv. Synth. Catal.
Both results, activity and selectivity, are in agreement with a 347 (2005) 1404–1412.
mechanism involving a p-bond activation and a double coordina- [35] E.T. Silveira, A.P. Umpierre, L.M. Rossi, G. Machado, J. Morais, G.V. Soares, I.J.R.
tion of diene substrates, necessitating several neighbouring surface Baumvol, S.R. Teixeira, P.F.P. Fichtner, J. Dupont, Chem. Eur. J. 10 (2004) 3734–
3740.
atoms only found in facial positions on the larger NPs. Further- [36] K. Philippot, B. Chaudret, C.R. Chimie 6 (2003) 1019–1034.
more, these RuNPs show a high level of recyclability with neither [37] N. Bedford, C. Dablemont, G. Viau, P. Chupas, V. Petkov, J. Phys. Chem. C 111
loss of activity nor significant agglomeration. (2007) 18214–18219.
[38] R. Nyholm, N. Martensson, J. Phys. Chem. 13 (1980) L279.
To conclude, in olefin hydrogenation by ruthenium nanoparti- [39] J.A. Van Bokhoven, J.T. Miller, J. Phys. Chem. C 111 (2007) 9245.
cles in ionic liquid media, both reactivity and selectivity are signif- [40] V.A. Finkel, M.I. Palatnik, G.P. Kovtun, Phys. Met. Metall. 32 (1971) 231.
icantly dependent on the nanoparticle size. [41] R.A. Van Santen, Acc. Chem. Res. 42 (2009) 57–66.
[42] A. Denicourt-Nowicki, A. Ponchel, E. Monflier, A. Roucoux, Dalton Trans. 48
(2007) 5714–5719.
Acknowledgments [43] D.Y. Murzin, Chem. Eng. Sci. 64 (2009) 1046–1052.
[44] A. Binder, M. Seipenbusch, M. Muhler, G. Kasper, J. Catal. 268 (2009) 150–155.
[45] N. Semagina, A. Renken, L. Kiwi-Minsker, J. Phys. Chem. C 111 (2007) 13933–
P.S.C. acknowledges the Ph.D. grant attributed by the Ministère 13937.
de l’Enseignement Supérieur et de la Recherche, France, and the EU [46] M. Saeys, M.-F. Reyniers, M. Neurock, G.B. Marin, Surf. Sci. 600 (2006) 3121–
transnational access programme. A.P. thanks the post-doctoral 3134.
[47] W.L. Manner, G.S. Girolami, R.G. Nuzzo, J. Phys. Chem. B 102 (1998) 10295–
grant by the project ANR CALIST. This work has been funded by 10306.
CNRS and ANR (ANR Project CALIST, ANR-07-CP2D-02-03). [48] J. Silvestre-Albero, G. Rupprechter, H.-J. Freund, J. Catal. 240 (2006) 58–65.
[49] H. Arakawa, K. Takeuchi, T. Matsuzaki, Y. Sugi, Chem. Lett. 13 (1984) 1607.
[50] T. Hanaoka, H. Arakawa, T. Matsuzaki, Y. Sugi, K. Kanno, Y. Abe, Catal. Today 58
Appendix A. Supplementary data (2000) 271.
[51] S. Zhou, H. Zhao, D. Ma, S. Miao, M. Cheng, X. Bao, Z. Phys. Chem. 219 (2005) 949.
[52] J. Gavnholt, J. Schiotz, Phys. Rev. B 77 (2008) 035404/035401–035404/035410.
Supplementary data associated with this article can be found, in [53] M.V. Seregina, L.M. Bronstein, O.A. Platonova, D.M. Chernyshov, P.M. Valetsky,
the online version, at doi:10.1016/j.jcat.2010.07.018. J.r. Hartmann, E. Wenz, M. Antonietti, Chem. Mater. 9 (1997) 923.
[54] J. Huang, T. Jiang, H. Gao, B. Han, Z. Liu, W. Wu, Y. Chang, G. Zhao, Angew. [60] P.J. Dyson, G. Laurenczy, C.A. Ohlin, J. Vallance, T. Welton, Chem. Commun.
Chem. Int. Ed. 43 (2004) 1397–1399. (2003) 2418–2419.
[55] G. Ertl, H. Knozinger, J. Weitkamp (Eds.), Handbook of Heterogeneous [61] J. Jacquemin, M.F. Costa Gomes, P. Husson, V. Majer, J. Chem. Thermodyn. 38
Catalysis, Wiley-VCH, Weinheim, 1997. (2006) 490–502.
[56] J. Dupont, G.S. Fonseca, A.P. Umpierre, P.F.P. Fichtner, S.R. Teixeira, J. Am. [62] J. Jacquemin, P. Husson, V. Majer, M.F. Costa Gomes, Fluid Phase Equilib. 240
Chem. Soc. 124 (2002) 4228–4229. (2006) 87.
[57] P.J. Dyson, Appl. Organomet. Chem. 16 (2002) 495–500. [63] J. Jacquemin, P. Husson, V. Majer, M.F. Costa Gomes, J. Solution Chem. 36
[58] P.J. Dyson, in: a.M.T.J. Mc Cleverty (Ed.), Comprehensive Coordination (2007) 967–979.
Chemistry II, Elsevier, Amsterdam, pp. 557–566. [64] P. Migowski, D. Zanchet, G. Machado, M.A. Gelesky, S.r.R. Teixeira, J. Dupont,
[59] P.J. Dyson, D. Zhao, Multiphase Homogeneous Catalysis, Wiley-VCH, Phys. Chem. Chem. Phys. 12 (2010) 6826–6833.
Weinheim, pp. 494–511. [65] D. Li, R.B. Kaner, J. Am. Chem. Soc. 128 (2006) 968–975.
tel-00708600, version 1 - 15 Jun 2012
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PAPER www.rsc.org/nanoscale | Nanoscale
Imidazolium ionic liquids as promoters and stabilising agents for the

preparation of metal(0) nanoparticles by reduction and decomposition of
organometallic complexes
Martin H. G. Prechtl,†*a Paul S. Campbell,b Jackson D. Scholten,a Georgina B. Fraser,b Giovanna Machado,c
Catherine C. Santini,*b Jairton Dupont*a and Yves Chauvinb
Received 9th August 2010, Accepted 1st September 2010
DOI: 10.1039/c0nr00574f
The organometallic complexes ([Ru(COD)(2-methylallyl)2] and [Ni(COD)2] (COD ¼ 1,5-

Jun 2012 | doi:10.1039/C0NR00574F
cyclooctadiene) dissolved in imidazolium ionic liquids (ILs) undergo reduction and decomposition,
respectively, to afford stable ruthenium and nickel metal(0) nanoparticles (Ru(0)-NPs and Ni(0)-NPs)
in the absence of classical reducing agents. Depending on the case, the reduction/auto-decomposition is
promoted by either the cation and/or anion of the neat imidazolium ILs.
Introduction (COD ¼ 1,5-cyclooctadiene) and [Ni(COD)2] under very mild

conditions. In these studies the role of both anion and cation is
In recent years, ILs have proven their versatility in synthetic and
15http://pubs.rsc.org
addressed and reaction pathways for the reduction/decomposi-

catalytic applications, provoking ever-growing interest in both tion processes are proposed.
Downloaded on 10 November 2010
academic and industrial research. One particularly intriguing

field is the synthesis of nanoscale metal catalysts of controlled
size and shape, namely metal(0) nanoparticles (M-NPs).1–4 ILs Results and discussion
have unique and tuneable properties useful in the synthesis of M-
1 - on
NPs via chemical routes. This can be controlled simply by The formation of Ru(0)-NPs using standard protocol with
08 October 2010
incorporating coordinating groups,5–7 varying the coordination [Ru(COD)(2-methylallyl)2] in IL (i.e. under 4 bar hydrogen at
50 C)7,14 was accompanied by the evolution of small amounts of
Published onversion
strength of the anion,8,9 or changing the length of the alkyl-chain

in the cation.10–15 In general, appropriate metal complexes or odorous by-products (characteristic of ammonia/amines). This
metal salts are dispersed/dissolved in the IL and subsequently odour was particularly intense in the ILs BMI$NTf2 and
reduced to the corresponding M-NPs, in the ubiquitous presence HM2I$NTf2 (Fig. 1).
tel-00708600,
of reducing reagents such as molecular hydrogen gas, complex The volatiles were thus analysed online in the gas phase with
hydrides (NaBH4 and LiAlH4), hydrazine,1–4 alcohols,16 and a mass gas-analyser. Indeed, compounds were detected with
thiols.17 In some cases, the IL itself can carry the reducing agent, masses that could be assigned to small molecules formed due to
e.g. hydroxylated imidazolium salts,18,19 and depending on the the fragmentation of the imidazolium ring, such as acetonitrile/
redox potential of the metal precursor, the imidazolium cation isocyanomethane (M+ ¼ 41), methylamine (M+ ¼ 29, MeN),
may even undergo oxidation. For example, in the case of Au(III), ethylene (M+ ¼ 28) and hydrogen cyanide (M+ ¼ 27). Moreover,
the imidazolium cation itself can act as a reducing agent to yield the observed C4-fragment signals (M+ ¼ 56–58) provide strong
prismatic gold particles in BMI$PF6.20 evidence for the decomposition of the ruthenium complex
The preparation of M-NPs in ILs by simple decomposition of [Ru(COD)(2-methylallyl)2] involving the formation of isobutene/
organometallic compounds in their formal zero oxidation states isobutane from the 2-methylallyl-ligand in the Ru(II) complex.
is invariably performed in the presence of hydrogen11,21,22 or Interestingly, the fragmentation of the IL seems to occur only
under thermal8,15,23 or photolytic9 conditions. during the reduction of Ru complex, but it is not promoted by
In this work, we report a novel approach for the synthesis of the Ru(0)-NPs. The gaseous by-products were exclusively
Ru(0)- and Ni(0)-NPs in imidazolium ILs, which act as detected during the NP synthesis, but not when Ru(0)-NPs were
incommensurably mild reducing/decomposing reagents for the stirred in BMI$NTf2 and HM2I$NTf2 for a prolonged duration
organometallic complexes [Ru(COD)(2-methylallyl)2] (several days) under identical conditions. A similar observation
for the imidazolium ring fragmentation has previously been
made, during the ultrasonic irradiation of imidazolium chloride
a
Laboratory of Molecular Catalysis, Institute of Chemistry, Universidade
Federal do Rio Grande do Sul, Av. Bento Gonçalves 9500, 91501-970
Porto Alegre, RS, Brazil. E-mail: jairton.dupont@ufrgs.br; Fax: +55 51
33087304; Tel: +55 51 33086321
b
Universit
e de Lyon, Institut de Chimie de Lyon, C2P2, UMR 5265
CNRS—ESCPE Lyon, 43 bd du 11 Novembre 1918, F-69626
Villeurbanne Cedex, France. E-mail: santini@cpe.fr
c
Centro de Tecnologias Estrategicas do Nordeste—CETENE, 50740-540
Recife, PE, Brazil
† Present address: Humboldt University Berlin, Brook-Taylor-Strasse 2,
12489 Berlin, Germany. E-mail: . E-mail: martin.prechtl@hu-berlin.de Fig. 1 Structure of the ILs used in this study.
This journal is ª The Royal Society of Chemistry 2010 Nanoscale

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at 135 C, causing degradation of ILs.24–26 However, herein the were similar to those of Ru(0)-NPs previously generated
observed decomposition of the imidazolium ring is not clearly using hydrogen gas as a reducing agent for the reduction
understood. of [Ru(COD)(2-methylallyl)2] or decomposition of
More interestingly, further investigations of the Ru(II)/IL [Ru(COD)(COT)] (COT ¼ 1,3,5-cyclooctatriene).7,11,14,22
reaction system revealed a more important result: the presence of The Ru(0)-NP formation led us to propose a reaction pathway
hydrogen gas as a reducing reagent for the Ru complex seems to in which the imidazolium ILs BMI$NTf2 and HM2I$NTf2 might
be obsolete. Stirring a mixture of the complex in HM2I$NTf2 act as reducing agents for [Ru(COD)(2-methylallyl)2]. Here the
under argon atmosphere at 50 C for a prolonged period (2 days) NTf2 anion would act as a nucleophile27,28 and attack the allylic-
resulted in a dark brown/black colloidal solution. Samples for ligand of the complex (Schemes 1 and 2).
TEM analysis were prepared by placing a small amount of the This stoichiometric reaction would cause the concomitant
Ru(0)-NPs dispersed in HM2I$NTf2 onto a holey carbon film reduction of the Ru(II) complex and subsequent decomposition
supported by a copper grid. The diameters of the particles in the of the IL. Consequently, the ruthenium would lose its ligand-
micrographs were measured using the software Sigma Scan Pro sphere and be reduced to ruthenium(0) atoms that coalesce
Jun 2012 | doi:10.1039/C0NR00574F
5. Size distribution histograms of the NPs were obtained by generating the Ru(0)-NPs. It is proposed that during the reduc-
measuring the diameter of randomly selected particles, resulting tion process of the Ru(II) complex, the first step involves a ligand
in the particle size of 2.0 0.3 nm (see Fig. 2) with a monomodal exchange between the COD and a stronger coordinating ligand,
distribution. occurring readily under the given reaction conditions.29 A
The crystalline structure of the particles was confirmed by HR- stronger coordinating ligand is easily provided in neat imidazo-
TEM micrographs, analysed using Gatan Digital Micrograph lium ionic liquid as solvent, where classical and abnormal
Software. By means of HR-TEM measurements it was possible N-heterocyclic carbenes (NHCs) formed in situ might act as
to obtain the Fourier transform images from which lattice a ligand.30,31 As a consequence, the NTf2 anion would ‘‘lose’’ its
spacings of 2.04 Å and 2.13 Å were measured. These lattice counterion, thus enhancing its nucleophilicity. And this would
spacings correspond to the interplanar distances (1 0 1) and favour its subsequent attack on the allylic species of the Ru(II)
(0 0 2), respectively, of hcp Ru(0). Isolation of the Ru(0)-NPs for complex. The resulting ruthenium(0) metal atoms in the IL go on
analysis by XRD was not possible, corroborating previous to generate the M-NPs. The isobutene by-product was detected
reports.14,22 The size and size distribution of the ruthenium NPs by MS analysis of the gas phase (see above). However, attempts
1 - on
to detect the hypothesised by-product N-isobutene N-triflate in

08 October 2010
the liquid-phase by NMR were unsuccessful, presumably due to

the very low concentration.
Published onversion
tel-00708600,
Scheme 1 Formation of Ru(0)-NPs in HM2I$NTf2.
Fig. 2 Selected TEM image of Ru(0)-NPs (2.0 0.3 nm) in HM2I$NTf2 Scheme 2 Proposed reductive elimination of the allyl-ligand induced by
and the histogram of the NPs size distribution. the NTf2 anion (L ¼ ligand/solvent-IL).
Nanoscale This journal is ª The Royal Society of Chemistry 2010

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To prove this pathway, the anion-effect in different imidazo-

lium ILs was therefore investigated. When using the IL BMI$BF4
(BF4 ¼ tetrafluoroborate), for example, a green suspension that
showed no indication of IL decomposition or Ru(0)-NPs
formation was obtained. Also, using EMI$B(CN)4 and
BMI$N(CN)2, the strongly coordinating nature of the anions
prevented the reduction of the Ru(II) complex and the reaction
solution remained clear and colourless, even when subjected to
a longer reaction time (5 days). Furthermore, the typical catalytic
properties of nanoscale ruthenium catalysts in arene hydroge-
nation were tested with these Ru/IL-systems.14 Indeed, the
Ru(0)-NPs produced in HM2I$NTf2 showed the highest activity
in toluene hydrogenation, resulting in conversions above 95%
Jun 2012 | doi:10.1039/C0NR00574F
(4 bar H2 at 75 C, 18 h), similar to results previously reported.14

The Ru(0)-NPs in BMI$NTf2 were also active in toluene
hydrogenation, but with a poorer conversion (55%) under the
same conditions. In addition, the systems using the ILs
BMI$BF4, EMI$B(CN)4 and BMI$N(CN)2 were subjected to Fig. 3 Sponge-like agglomerates of Ni(0)-NPs formed by auto-decom-
identical conditions, to gauge whether Ru(0)-NPs would form position of [Ni(COD)2] in BMI$NTf2.
in situ during toluene hydrogenation. Indeed, the green suspen-
sion in BMI$BF4 turned dark brown and the toluene was
hydrogenated, albeit with low conversion (<20%), indicating the

formation of Ru(0)-NPs. In contrast, the clear solutions in

EMI$B(CN)4 and BMI$N(CN)2 turned slightly yellow, but no
hydrogenation of toluene was observed.
The stability of [Ni(COD)2] in imidazolium ILs was also
1 - on
investigated. This complex can be easily decomposed affording

08 October 2010
Ni(0)-NPs under hydrogen in organic solvents such as THF, in

the presence of hexadecylamine (HDA) as the stabilising ligand
Published onversion
or polyvinylpyrrolidone (PVP) as the polymer support.32,33 In

this case, cyclooctane is produced as a side product. Moreover,
Ni(0)-NPs from the decomposition of [Ni(COD)2] under
tel-00708600,
hydrogen in imidazolium-based ILs have also been reported.12,34

However, it is worth noting that in this previous work
a substantial amount of benzene was used to aid the dissolution Scheme 3 Mechanism for the isomerisation of COD necessitating a Ni–
of [Ni(COD)2] (6 mL of benzene for 2 mL of IL), and although H specie.
effort was made to remove the volatiles before decomposition, it
is not possible to be sure of the complete removal of benzene and
therefore the media in which the decomposition actually With Ru(0)-NPs, the presence of surface hydrides has been
occurred.12,34 proven by hydrogenation of ethylene without the addition of H2
In this work, spontaneous decomposition of [Ni(COD)2] by a solution of Ru(0)-NPs in IL.35 This experiment was repeated
occurred upon dissolution at 25 C, in both EMI$NTf2 and for the Ni(0)-NPs formed by auto-decomposition of [Ni(COD)2]
BMI$NTf2, in the absence of hydrogen. TEM was performed on in BMI$NTf2. After treatment under ethylene atmosphere
the resulting black solutions and revealed in each case a mixture (4 bars, 100 C, 24 h) no ethane was detected by GC as a result of
of Ni(0)-NPs (<10 nm) and sponge-like agglomerates of larger ethylene hydrogenation, however, significant amounts of butenes
particles (Fig. 3). It can be seen from the TEM image that these and hexenes were detected, probably a result of oligomerisation
sponge-like structures clearly consist of agglomerates of indi- of the ethylene. Interestingly, the formation of an ethyl
vidual particles. This is completely different from previous substituted IL BMEI$NTf2 (BMEI ¼ 1-n-butyl-2-ethyl-3-meth-
findings, highlighting the important role of co-solvents.12,34 ylimidazolium) was also observed by NMR spectroscopies
Notably 1H NMR spectroscopy and gas chromatography (COSY, HETCOR and DOSY) and confirmed by electrospray
performed on the resulting solution showed only a trace of mass spectrometry where cations at m/z ¼ 139 and 167 were
cyclooctane, resulting from the hydrogenation of 1,5-COD observed with similar abundances, corresponding to [BMI]+ and
ligand, the by-product of decomposition reported in the litera- [BMEI]+, respectively. A small amount of the cation [B2MI]+
ture.32,33 Instead, the presence of both 1,5-COD and its isomer (B2MI ¼ 1,2-di-n-butyl-3-methylimidazolium) was also observed
1,3-cyclooctadiene (1,3-COD) was detected by both gas chro- by mass spectrometry, m/z ¼ 195, probably a result of oligo-
matography and 1H/13C NMR spectroscopy. 1,3-COD must be merisation of ethylene to 1-butene before reaction with the imi-
a result of the isomerisation of 1,5-COD, which could only take dazolium cycle. The evidence gathered suggests that the observed
place at a metal centre in the presence of Ni–H bond decomposition could be due to the cleavage of the very acidic
(Scheme 3). C2–H bond and the consequent in situ generation of NHC

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species, as already reported in the case of Ir(0)-NP preparation in

ILs,36–40 and with homogeneous complexes of Ni,41 Pd,42–44
Rh,30,45 and Ir.45 Cavell and co-workers have proposed a mech-
anism for the possible catalytic cycle for the imidazolium/alkene
coupling reaction where the organometallic starting material was
[Ni(OAc)2].46 The same phenomenon has also been observed in
work by Lecocq and Olivier-Bourbigou who were investigating
the oligomerisation behaviour of Ni in imidazolium ILs.41 At this
point it is impossible to determine whether the observed reactions
(isomerisation of COD and formation of BMEI$NTf2) occur on
molecular or colloidal species. However, these results do prove
that the cleavage of the C2–H bond occurs during the sponta-
neous decomposition on dissolution. The proposed mechanism
Jun 2012 | doi:10.1039/C0NR00574F
of the reaction of imidazolium salts with low valent M(0)

(M ¼ Pd and Ni) hypothesises the formation of a molecular
carbene–M–H species, as also proposed in the catalytic cycle for
oligomerisation and formation of trialkylimidazolium
species.47,48 The presence of bis(imidazolylidene)nickel complexes
[(NHC)2NiH]+ was also detected by mass spectrometry, implying
that a molecular intermediate is in fact present as proposed. This
may act as a transient species and could be the active species for
the above mentioned reactions. Similar bis-carbene iodide nickel

complexes have already been prepared in imidazolium ILs and

isolated by Wasserscheid’s group.46 These were indeed found to
be active in the dimerisation of butene carried out in ILs,
although no production of Ni(0)-NPs was noted here, perhaps
1 - on
due to the presence of the strongly coordinating iodides.

08 October 2010
Although the exact mechanism remains unclear, from our

Fig. 4 TEM image of Ni(0)-NPs (7.0 2.0 nm) formed by auto-
investigations it is certain that the spontaneous decomposition of
Published onversion
decomposition of [Ni(COD)2] in BM2I$NTf2 and size distribution

[Ni(COD)2] on dissolution into the ILs with short alkyl chains histogram.
involves attack on the acidic C2–H (Scheme 4).
To achieve the controlled generation of small-size Ni(0)-NPs,
tel-00708600,
we must find a way of inhibiting this auto-decomposition in the case of [Ru(COD)(2-methylallyl)2] the decomposition of
imidazolium ILs with short alkyl chains. Another strategy [Ni(COD)2] in BMI$BF4 occurred not spontaneously but very
attempted in order to circumvent the problem was to use an IL slowly at 25 C only under 4 bar of H2, once again highlighting
which does not contain the most acidic C2–H proton such as the importance of the NTf2-anion. Therefore, as the auto-
BM2I$NTf2. Surprisingly, the [Ni(COD)2] still decomposed on decomposition of [Ni(COD)2] to Ni(0)-NPs was also observed
stirring, but this time afforded well dispersed Ni(0)-NPs (7.0 uniquely in NTf2-ILs, it is possible that the NTf2 anion inter-
2.0 nm, Fig. 4). This can only be explained by attack on the two venes in the Ni(0)-NP formation through interaction with the
less acidic protons C4–H, C5–H of the imidazolium ring and COD ligands, similarly to the case of the Ru(II) complex.
generation of transient non-classical NHC ligands.31
In another attempt to avoid auto-decomposition the
Conclusions
NTf2-anion was exchanged for the more strongly coordinating
BF4-anion, yielding important results. In this case, similarly to In summary, IL decomposition and simultaneous Ru(0)-NP
formation are limited to imidazolium salts containing the NTf2
anion. These results may explain how the Ru(0)-NPs formation is
induced by imidazolium N-triflate ILs, but cannot explain the
exact mechanism for the imidazolium ring fragmentation in small
quantities. Most importantly, the formation of small-sized active
ruthenium nanoscale hydrogenation catalysts is possible at low
temperature and atmospheric pressure in the absence of classical
and potentially dangerous reducing agents such as hydrogen gas
(under elevated pressure), pyrophoric LiAlH4 or hazardous
hydrazine. Moreover, an unexpected spontaneous decomposition
of [Ni(COD)2] occurred without the addition of hydrogen for
imidazolium ILs with short alkyl chains: ILs BMI$NTf2,
EMI$NTf2 and BM2I$NTf2. In the case of ILs BMI$NTf2 and
Scheme 4 Reactions occurring during the auto-decomposition of EMI$NTf2, TEM micrographs showed that Ni(0)-NPs of fairly
[Ni(COD)2] in imidazolium ILs. large diameter were formed as well as sponge-like super

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agglomerates. However, for IL BM2I$NTf2 well dispersed Ni(0)- Then, the IL HM2I$NTf2 (1.5 mL) was added via syringe under
NPs are formed. An explanation for the activation of the acidic an argon flow. The mixture was stirred at room temperature for
protons on the imidazolium ring and the subsequent NHC 60 min, resulting in a turbid dispersion. The system was heated to
formation that led to a rapid decomposition of the complex has 50 C, and stirred under argon for two days resulting in a black
been proposed. The additional interaction between the NTf2 suspension. The Fischer–Porter bottle was connected to a mass
anion and the COD ligands on the Ni complex, which also may gas-analyser in order to evaluate the gas phase. After analysis the
support the Ni(0)-NPs formation, cannot be excluded nonethe- Fischer–Porter bottle was then kept under reduced pressure to
less. It is conceivable that this novel approach may be extended as eliminate the organic volatiles formed. An aliquot of the Ru(0)-
a general access to M-NPs in imidazolium NTf2-ILs, starting from NPs embedded in the IL was analysed by TEM.
organometallic complexes bearing only COD, allylic and/or
olefinic ligands, such as [Co(COD)2], [Ru(COD)(COT)],
Synthesis of Ni(0)-NPs
[Rh(allyl)3], [Pd(COD)2], [Pt(COD)2] or [Pt(norbornene)3].
[Ni(COD)2] (50 mg, 0.14 mmol) was stirred under argon in the
Jun 2012 | doi:10.1039/C0NR00574F
Experimental ILs BMI$NTf2, EMI$NTf2 and BM2I$NTf2 (10 mL) producing

a pale yellow solution at 25 C. After 1 h the solution had turned
General green and after a further hour a black solution resulted. Samples
All manipulations were carried out under argon atmosphere. The for TEM observations were prepared by placing a thin film of the
organometallic complexes [Ru(COD)(2-methylallyl)2] and Ni(0)-NPs dispersed in ILs on a copper grid coated with holey
[Ni(COD)2] were purchased from Sigma-Aldrich and Strem carbon film.
Chemicals, respectively. For the ruthenium experiments, a Hiden
QIC20 MS-QTOF gas-analyser was used for the gas phase
Oligomerisation of ethylene by Ni(0)-NPs in IL

analysis after the synthesis of Ru(0)-NPs. TEM analyses were
performed in a JEOL-JEM 2010 microscope operating at 200 kV A 2 mL sample of the Ni(0)-NPs solution in the IL was intro-
(UFRGS-CME, Brazil) and EDS, and used for catalytic experi- duced under argon into a Schlenk of known volume. The sample
ments as previously described.14 The HR-TEM was performed at was treated under flow of argon for 18 h. The argon atmosphere
the ‘‘Centro de Tecnologias Estrat egicas do Nordeste’’ was replaced with a known pressure of ethylene using a vacuum
1 - on
(CETENE), Recife/Brazil. The ILs were synthesised as previ- line and the system was stirred. A decrease of the internal pres-
08 October 2010
ously reported,49 and ILs EMI$B(CN)4 and BMI$N(CN)2 were sure was observed, and the composition of the gas phase was
monitored by gas chromatography. After 12 h, the atmosphere
Published onversion
purchased from Merck KGaA, Germany.

In the case of nickel experiments, conventional TEM micro- was replaced by a H2 atmosphere and the system was heated and
graphs were obtained at the ‘‘Centre Technologique des Micro- stirred for 12 h. The composition of the gas phase was again
structures’’, France, using a Philips 120 CX electron microscope monitored by gas chromatography.
tel-00708600,
operating at 120 kV. Size distribution histograms were con-

structed from the measurement of at least 200 different NPs Acknowledgements
assuming a near spherical shape and random orientation. Solu-
tion NMR spectra were recorded on Bruker Avance 300 MHz This work was funded by ANR project CALIST (ANR-07-
spectrometer for 1H and 13C. DRX 500 MHz for 2H. Gas phase CP2D-02-03), the ‘‘Ministere de l’enseignement superieur et de la
1
H NMR spectra were obtained on a Bruker DRX 500 instru- recherche’’ (P.S.C.), CNPq, CAPES, INCT-Catal. and the
ment at 298 K (nominal). Mass spectra were acquired on Alexander-von-Humboldt Foundation (M. H. G. Prechtl).
a ThermoFinnigan LCQ Advantage ion trap instrument, G.B.F. acknowledges the grant attributed by the Erasmus
detecting positive (+) and negative (ÿ) ions in the ESI mode. programme.
Samples (1 to 10 mg mLÿ1 in acetonitrile) were infused directly
into the source (5 mL minÿ1) using a syringe pump. The following References
source parameters were applied: spray voltage 3.0–3.5 kV,
1 J. Dupont and J. D. Scholten, Chem. Soc. Rev., 2010, 39, 1780–1804.
nitrogen sheath gas flow 5–20 arbitrary units. The heated capil- 2 P. Migowski and J. Dupont, Chem.–Eur. J., 2007, 13, 32–39.
lary was held at 200 C. MS spectra were obtained by applying 3 H. Boennemann and K. S. Nagabhushana, Nanoclusters in Catalysis
a relative collision energy of 25 to 40% of the instrumental and Materials Science: the Issue of Size Control, ed. B. Corain,
maximum. The products were quantitatively analysed by gas G. Schmid and N. Toshima, Elsevier B.V., Amsterdam, 2008, pp.
21–48.
chromatography on a P6890 chromatograph equipped with 4 H. Boennemann, K. S. Nagabhushana and R. M. Richards,
a flame ionisation detector (FID) and an Al2O3/KCl column Nanoparticles and Catalysis, Wiley-VCH, Weinheim, 2008.
(L: 50 m, diameter: 0.32 mm, and film thickness: 5 mm). The 5 Y. G. Cui, I. Biondi, M. Chaubey, X. Yang, Z. F. Fei, R. Scopelliti,
C. G. Hartinger, Y. D. Li, C. Chiappe and P. J. Dyson, Phys. Chem.
injector and detector temperature was 230 C, and the injection
Chem. Phys., 2010, 12, 1834–1841.
volume was 1 mL. The temperature was fixed at 190 C. The 6 Z. F. Fei, D. B. Zhao, D. Pieraccini, W. H. Ang, T. J. Geldbach,
synthesis of ILs was carried out as previously reported.43 R. Scopelliti, C. Chiappe and P. J. Dyson, Organometallics, 2007,
26, 1588–1598.
7 M. H. G. Prechtl, J. D. Scholten and J. Dupont, J. Mol. Catal. A:
Synthesis of Ru(0)-NPs Chem., 2009, 313, 74–78.
8 E. Redel, R. Thomann and C. Janiak, Inorg. Chem., 2008, 47, 14–16.
In a typical experiment, a Fischer–Porter bottle was loaded with 9 E. Redel, R. Thomann and C. Janiak, Chem. Commun., 2008, 1789–
[Ru(COD)(2-methylallyl)2] (30 mg, 0.094 mmol) under argon. 1791.

View Online
10 P. S. Campbell, C. C. Santini, F. Bayard, Y. Chauvin, V. Colliere, 29 J. P. Genet, S. Mallart, C. Pinel, S. Juge and J. A. Laffitte,
A. Podgorsek, M. F. Costa Gomes and J. S a, J. Catal., 2010, 257, Tetrahedron: Asymmetry, 1991, 2, 43–46.
99–107. 30 J. D. Scholten and J. Dupont, Organometallics, 2008, 27, 4439–4442.
11 T. Gutel, C. C. Santini, K. Philippot, A. Padua, K. Pelzer, 31 S. Grundemann, A. Kovacevic, M. Albrecht, J. W. Faller and
B. Chaudret, Y. Chauvin and J. M. Basset, J. Mater. Chem., 2009, R. H. Crabtree, Chem. Commun., 2001, 2274–2275.
19, 3624–3631. 32 N. Cordente, C. Amiens, B. Chaudret, M. Respaud, F. Senocq and
12 P. Migowski, G. Machado, S. R. Texeira, M. C. M. Alves, J. Morais, M. J. Casanove, J. Appl. Phys., 2003, 94, 6358–6365.
A. Traverse and J. Dupont, Phys. Chem. Chem. Phys., 2007, 9, 4814– 33 N. Cordente, M. Respaud, F. Senocq, M. J. Casanove, C. Amiens and
4821. B. Chaudret, Nano Lett., 2001, 1, 565–568.
13 P. Migowski, D. Zanchet, G. Machado, M. A. Gelesky, S. R. Teixeira 34 P. Migowski, S. R. Teixeira, G. Machado, M. C. M. Alves, J. Geshev
and J. Dupont, Phys. Chem. Chem. Phys., 2010, 12, 6826–6833. and J. Dupont, J. Electron Spectrosc. Relat. Phenom., 2007, 156, 195–
14 M. H. G. Prechtl, M. Scariot, J. D. Scholten, G. Machado, 199.
S. R. Teixeira and J. Dupont, Inorg. Chem., 2008, 47, 8995–9001. 35 P. S. Campbell, C. C. Santini, D. Bouchu, B. Fenet, K. Philippot,
15 M. Scariot, D. O. Silva, J. D. Scholten, G. Machado, S. R. Teixeira, B. Chaudret, A. A. H. Padua and Y. Chauvin, Phys. Chem. Chem.
M. A. Novak, G. Ebeling and J. Dupont, Angew. Chem., Int. Ed., Phys., 2010, 12, 4217–4223.
2008, 47, 9075–9078. 36 L. S. Ott, S. Campbell, K. R. Seddon and R. G. Finke, Inorg. Chem.,
Jun 2012 | doi:10.1039/C0NR00574F
16 H. J. Ryu, L. Sanchez, H. A. Keul, A. Raj and M. R. Bockstaller, 2007, 46, 10335–10344.

Angew. Chem., Int. Ed., 2008, 47, 7639–7643. 37 L. S. Ott, M. L. Cline, M. Deetlefs, K. R. Seddon and R. G. Finke,
17 L. Zhao, C. Y. Zhang, L. Zhuo, Y. G. Zhang and J. Y. Ying, J. Am. J. Am. Chem. Soc., 2005, 127, 5758–5759.
Chem. Soc., 2008, 130, 12586–12587. 38 L. S. Ott and R. G. Finke, Inorg. Chem., 2006, 45, 8382–8393.
18 S. Choi, K. S. Kim, S. H. Yeon, J. H. Cha, H. Lee, C. J. Kim and 39 J. D. Scholten, G. Ebeling and J. Dupont, Dalton Trans., 2007, 5554–
I. D. Yoo, Korean J. Chem. Eng., 2007, 24, 856–859. 5560.
19 K. S. Kim, S. Choi, J. H. Cha, S. H. Yeon and H. Lee, J. Mater. 40 J. D. Scholten and J. Dupont, in Iridium Complexes in Organic
Chem., 2006, 16, 1315–1317. Synthesis, ed. L. A. Oro and C. Claver, Wiley-VCH Verlag GmbH
20 Y. Gao, A. Voigt, M. Zhou and K. Sundmacher, Eur. J. Inorg. Chem., & Co. KGaA, Weinheim, 2009, pp. 369–389.
2008, 3769–3775. 41 V. Lecocq and H. Olivier-Bourbigou, Oil Gas Sci. Technol., 2007, 62,
21 E. T. Silveira, A. P. Umpierre, L. M. Rossi, G. Machado, J. Morais, 761–773.

G. V. Soares, I. L. R. Baumvol, S. R. Teixeira, P. F. P. Fichtner and 42 C. M. Crudden and D. P. Allen, Coord. Chem. Rev., 2004, 248, 2247–
J. Dupont, Chem.–Eur. J., 2004, 10, 3734–3740. 2273.

22 T. Gutel, J. Garcia-Anton, K. Pelzer, K. Philippot, C. C. Santini, 43 L. Magna, Y. Chauvin, G. P. Niccolai and J. M. Basset,
Y. Chauvin, B. Chaudret and J. M. Basset, J. Mater. Chem., 2007, Organometallics, 2003, 22, 4418–4425.
17, 3290–3292. 44 M. H. G. Prechtl, J. D. Scholten and J. Dupont, Molecules, 2010, 15,
23 D. O. Silva, J. D. Scholten, M. A. Gelesky, S. R. Teixeira, 3441–3461.
1 - on
A. C. B. Dos Santos, E. F. Souza-Aguiar and J. Dupont, 45 U. Hintermair, T. Gutel, A. M. Z. Slawin, D. J. Cole-Hamilton,

08 October 2010
ChemSusChem, 2008, 1, 291–294. C. C. Santini and Y. Chauvin, J. Organomet. Chem., 2008, 693,
24 D. J. Flannigan, S. D. Hopkins and K. S. Suslick, J. Organomet. 2407–2414.
Published onversion
Chem., 2005, 690, 3513–3517. 46 D. S. McGuinness, W. Mueller, P. Wasserscheid, K. J. Cavell,

25 J. D. Oxley, T. Prozorov and K. S. Suslick, J. Am. Chem. Soc., 2003, B. W. Skelton, A. H. White and U. Englert, Organometallics, 2002,
125, 11138–11139. 21, 175–181.
26 S. Sowmiah, V. Srinivasadesikan, M. C. Tseng and Y. H. Chu, 47 N. D. Clement, K. J. Cavell, C. Jones and C. J. Elsevier, Angew.
Molecules, 2009, 14, 3780–3813. Chem., Int. Ed., 2004, 43, 1277–1279.
tel-00708600,
27 S. Chowdhury, R. S. Mohan and J. L. Scott, Tetrahedron, 2007, 63, 48 D. C. Graham, K. J. Cavell and B. F. Yates, Dalton Trans., 2007,
2363–2389. 4650–4658.
28 R. Bini, C. Chiappe, E. Marmugi and D. Pieraccini, Chem. Commun., 49 C. C. Cassol, G. Ebeling, B. Ferrera and J. Dupont, Adv. Synth.
2006, 897–899. Catal., 2006, 348, 243–248.

iii
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Appendix 3
Separation of Hafnium from

Zirconium in Ionic Liquids
235
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236
Appendix 3 Separation of Hafnium and Zirconium in Ionic Liquids
Separation of Zirconium from Hafnium in Ionic Liquids
The issue
Zirconium and hafnium occur naturally together, the most common ore being “zircon”. As
their chemical properties are very similar, extracting and separating highly pure metals is a
difficult challenge. In nuclear applications zirconium has a low neutron absorption cross-section
and is therefore a useful cladding material (“zircaloy”). Hafnium, on the other hand, has a high
neutron absorption cross-section (nearly 600 times that of zirconium). Therefore, for nuclear
applications, zirconium metal must contain less than 100 ppm hafnium. Three main processes are
in current use for the separation of zirconium from hafnium: multiple crystallization of potassium
zirconium fluoride; solvent extraction of the chlorides using methyl isobutyl ketone and water;
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extractive distillation of the chlorides using a KCl/AlCl3 molten salt bath at high temperature.1-11
These three processes present several severe drawbacks, e.g. recovery of oxide products,
corrosion problems, high running temperatures, etc. Hf/Zr separation is still a economic and
technical challenge (more than 60 papers published during the last decade, of which 25 % as
patents and from more than 20 different countries).12
Strategies
As part of this work, two strategies were attempted using ionic liquids with the ultimate
goal of achieving Zr/Hf separation with reduced hazards and process costs, as ILs are considered
as “green solvents”, due to some specific features such as non-flammability, high thermal
stability and non-volatility.13
1) Firstly, a novel range of imidazolium chlorometallate ionic liquids based on hafnium
and zirconium were synthesised and fully characterised. A difference in chemical or
physical properties of the resulting materials may have been exploited in their
extraction. The full characterisation of the new materials obtained is described in the
Dalton Transactions paper attached.
2) Secondly, it is reported in the literature that ZrCl4 and HfCl4 display a different
reactivity towards methyl-substituted aromatics; ZrCl4 produces a molecular complex,14
while reaction with HfCl4 results in an ionic species.15, 16 Thus the approach was to use
this difference in reactivity to undertake a subsequent liquid-liquid extraction, based on
237
Appendix 3 Separation of Hafnium and Zirconium in Ionic Liquids
the potential high solubility of the ionic complex in an ionic liquid compared to an
organic solvent. The preliminary positive results, for which a patent application has
been submitted, are described in the Chimica Oggi paper, also included in this
appendix.
References
[1] B. Prakash, C. V. Sundaram, Met. Mater. Proc. 2009, 21, 21.
[2] V. Ogarev, A. Skotnicki, B. Ninham, ,, Patent AU. 20080527. 2009, 12pp.
[3] L. A. Niselson, E. A. Egorov, E. L. Chuvilina, O. A. Arzhatkina, V. D. Fedorov, J. Chem.
Eng., 2009, 54, 726.
[4] M. Smolik, A. Jakobik-Kolon, M. Poranski, Hydrometallurgy, 2009, 95, 350.
tel-00708600, version 1 - 15 Jun 2012
[5] K. Saberyan, A. H. Meysami, F. Rashchi, E. Zolfonoun, Chin. J. Chem., 2008, 26, 2067.
[6] M. Taghizadeh, R. Ghasemzadeh, S. N. Ashrafizadeh, K. Saberyan, M. G. Maragheh,
Hydrometallurgy, 2008, 90, 115.
[7] L. Delons, G. Picard, D. Tigreat, Compagnie Europeenne Du Zirconium Cezus, WO
20020412. 2002, 20 pp.
[8] L. Delons, S. Lagarde, A. Favre Reguillon, S. Pellet Rostaing, M. Lemaire, L. Poriel,
Compagnie Europeenne du Zirconium-Cezus, Fr. Fr 2004-7721 2006, 40.
[9] J. A. Sommers, J. G. Perrine, US, ATI Properties, Inc., USA, 20020129. 2003, 8 pp.
[10] N. Ozanne, M. L. Lemaire, A. Guy, J. Foos, S. Pellet-Rostaing, F. Chitry, WO,
Compagnie Europeenne du Zirconium Cezus, Fr., 20010910. 2002, 23 pp.
[11] A. Da Silva, E. El-Ammouri, P. A. Distin, Can. Metall. Q. 2000, 39, 37.
[12] R. H. Nielsen, in KIRK OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY
John Wiley & Sons, New York, 2004.
[13] P. Wasserscheid, T. Welton, Ionic liquids in synthesis, Wiley-VCH, Weinheim, 2008.
[14] F. Musso, E. Solari, C. Floriani, K. Schenk, Organometallics 1997, 16, 4889.
[15] F. Calderazzo, I. Ferri, G. Pampaloni, S. Troyanov, J. Organomet. Chem., 1996, 518,
189.
[16] F. Calderazzo, P. Pallavicini, G. Pampaloni, P. F. Zanazzi, J. Chem. Soc., Dalton Trans.,
1990, 2743.
238
PAPER www.rsc.org/dalton | Dalton Transactions
Synthesis and characterisation of ionic liquids based on

1-butyl-3-methylimidazolium chloride and MCl4 , M = Hf and Zr†
Paul S. Campbell,a Catherine C. Santini,*a Denis Bouchu,b Bernard Fenet,c Leszek Rycerz,d Yves Chauvin,a
Marcelle Gaune-Escard,e Catherine Bessada f and Anne-Laure Rollet f ,g
Received 15th September 2009, Accepted 26th October 2009
First published as an Advance Article on the web 1st December 2009
DOI: 10.1039/b919094e
Dialkylimidazolium chlorometallate molten salts resulting from the combination of zirconium or

hafnium tetrachloride and 1-butyl-3-methylimidazolium chloride, [C1 C4 Im][Cl], have been prepared
with a molar fraction of MCl4 , R = nMCl4 /nMCl4 + n[C1C4IM][Cl] equal to 0, 0.1, 0.2, 0.33, 0.5, 0.67. The
structure and composition were studied by Differential Scanning Calorimetry (DSC), 35 Cl (263 to 333
K), 1 H and 13 C solid state and solution NMR spectroscopy, and electrospray ionisation (ESI) mass
spectrometry. The primary anions of the MCl4 -based ILs were [MCl5 ], [MCl6 ] and [M2 Cl9 ], whose
relative abundances varied with R. For R = 0.33, pure solid [C1 C4 Im]2 [MCl6 ], for both M = Zr and Hf
are formed (m.p. = 366 and 385 K, respectively). For R = 0.67 pure ionic liquids [C1 C4 Im][M2 Cl9 ] for
both M = Zr and Hf are formed (T g = 224 and 220 K, respectively). The thermal dissociation has been
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attempted of [C1 C4 Im]2 [HfCl6 ], and [C1 C4 Im]2 [ZrCl6 ] monitored by 35 Cl and 91 Zr solid NMR (high
temperature up to 551 K).
Introduction trochemical methods,11-15 showing the accessibility of the mono-,

di- and trinuclear anions, AlCl4 - , Al2 Cl7 - and Al3 Cl10 - with
During the past couple of decades, ionic liquids have undergone no more than two different species coexisting at any given
fast development for use in industrial chemical procedures, driven organochloride/AlCl3 ratio. Their utility in catalysis has been
by a need for more environmentally friendly solvents. From a proven in a number of recent publications.16-20
chemical engineering point of view, there are certain advantages In the literature, several imidazolium salts of less hydrolysable
offered by the properties of ionic liquids, notably the large range chlorides, based on iron,21-23 tin,22,24 zinc,19,22,24-27 copper,22 in-
of temperatures, high thermal conductivity and negligible vapour dium, gold,24,28,29 nickel,30 platinum,31 cobalt,30 manganese22 and
pressure. This means that they are completely non-volatile right up vanadium,32 have been reported.
to their temperature of decomposition (typically above 573 K) and In group 4, imidazolium salts derived from Ti(IV) have recently
therefore the risk of solvent vapours escaping into the atmosphere been reported.33 However, only one imidazolium chlorozirconate,
is considerably reduced. [C1 C4 Im]2 [ZrCl6 ], is described,22 although these chlorometallates
The development of acidic ionic liquids, derived from metal may be studied for the separation Hf/Zr which is still an economic
halides, as replacement for traditional acids has received and technical challenge.34
significant attention.1-6 Since the first chloroaluminate of This paper describes the synthesis and full characterisation
N-butylpyridinium,7 similar results have been obtained with salts [DSC, thermogravimetric analysis (TGA), 1 H, 13 C and 35 Cl NMR
of the N-alkylimidazolium cation. Chloroaluminate anions have spectroscopy, electrospray mass spectrometry] of a range of
been widely characterised by NMR spectroscopy (27 Al, 31 P and imidazolium salts based on ZrCl4 and HfCl4 and the study of
1
H),5,8-12 Raman scattering, UV and IR spectroscopies and elec- their thermal stability by high temperature 35 Cl and 91 Zr NMR
experiments.
a
Université de Lyon, Institut de Chimie de Lyon, UMR 5265 CNRS-
Université de Lyon-ESCPE Lyon, LC2P2, Equipe COMS, ESCPE 43
Boulevard du 11 Novembre 1918, 69616, Villeurbanne, France. E-mail:
santini@cpe.fr; Fax: +33(0)472431795; Tel: +33(0)472431794
b
Centre Commun de Spectrométrie de Masse, Université de Lyon, ESCPE,
Results and discussion
43 Boulevard du 11 Novembre 1918, F-69616 Villeurbanne, France
c The ionic liquids were prepared by a slow addition of solid
Centre Commun de RMN, Université de Lyon, ESCPE, 43 Boulevard du 11
Novembre 1918, F-69616 Villeurbanne, France anhydrous MCl4 into molten [C1 C4 Im][Cl] (338 K), and the
d
Chemical Metallurgy Group, Faculty of Chemistry, Wrocław University of mixture was kept at 338 K for 12 h under argon, Scheme 1, with R,
Technology, Wybreze Wyspianskiego 27, 50-370, Wrocław, Poland the molar fraction, i.e. the ratio of the number of moles of MCl4
e
Ecole Polytechnique, CNRS UMR 6595 Technopole de Chateau-Gombert divided by the sum of the number of moles of [C1 C4 Im][Cl] and
5 Rue Enrico Fermi, 13453, Marseille cedex 13, France
f MCl4 R = nMCl4 /nMCl4 + n[C1C4IM][Cl] with R = 0.1 ; 0.2 ; 0.33 ; 0.5
Université d’Orléans CEMHTI - CNRS UPR 3079, Orléans, France
g
Université Paris 06, UMR 7196, PECSA Paris, France and 0.67. As generally observed for all chlorometallates, for R =
† Electronic supplementary information (ESI) available: Experimental 0.33, 0.5 and 0.67 stoichiometric compounds have been obtained
details. See DOI: 10.1039/b919094e and fully characterised.
This journal is © The Royal Society of Chemistry 2010 Dalton Trans., 2010, 39, 1379–1388 | 1379
Scheme 1 The preparation of imidazolium chlorometallates.
DSC (differential scanning calorimetry)
This analysis was performed on the stoichiometric compounds.

Analytical samples (30–50 mg) were sealed in Pyrex°R ampoules
under reduced pressure of argon.
For R = 0.33, the results for [C1 C4 Im]2 [ZrCl6 ] and
[C1 C4 Im]2 [HfCl6 ], obtained with a heating and cooling rate of
5 K min-1 , are presented and compared to pure [C1 C4 Im]Cl in
Fig. 1. The values of temperature and enthalpy were determined
from measurements performed on three different samples for each
compound. A significant supercooling effect was observed during
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cooling. The following data were determined from DSC heating

curves. It was found that [C1 C4 Im]Cl melts congruently at 340 ±
1 K with a corresponding enthalpy Dfus H m = 22.9 ± 0.6 kJ mol-1 .
It should be pointed out that due to the supercooling effect,
crystallisation was not observed in the DSC cooling curve up
to 330 K, at which temperature the measurements were stopped
(Fig. 1a). [C1 C4 Im]2 [HfCl6 ], melts congruently at 385 ± 1 K with
enthalpy Dfus H m = 48.1 ± 1.1 kJ mol-1 . Due to supercooling,
crystallisation takes place at a lower temperature of about 362 K.
It is very likely that the analogous Zr compound, i.e.
[C1 C4 Im]2 [ZrCl6 ] also melts congruently at T fus = 366 ± 1 K
with a molar enthalpy Dfus H m = 21.5 ± 0.3 kJ mol-1 . However
a small additional endothermic effect at 391 K is observed in
the heating DSC curves (Fig. 1c). This could be indicative of
a small deviation from stoichiometry or the more complicated
behaviour of this compound (for example incongruent melting).
Additional measurements performed on this compound and
mixtures with molar fractions of [C1 C4 Im][Cl] larger and smaller
in comparison with [C1 C4 Im]2 [ZrCl6 ] planned in the near future,
would help to explain the phenomena connected with melting of
Fig. 1 DSC curves of (a) [C1 C4 Im]Cl, (b) [C1 C4 Im]2 [HfCl6 ], (c)
the [C1 C4 Im]2 [ZrCl6 ] compound.
[C1 C4 Im]2 [ZrCl6 ]: heating/cooling rate = 5 K min-1 .
For R = 0.67, DSC measurements performed on the samples
[C1 C4 Im][Hf2 Cl9 ] and [C1 C4 Im][Zr2 Cl9 ], showed only one thermal
effect corresponding to the glass transition. This transition
appears at T g = 225 K with Dcp = 0.098 J g-1 K-1 on heating, Fig. 2a,
and at T g = 220 K with Dcp = -0.081 J g-1 K-1 on cooling for the
hafnium compound. In the case of the zirconium compound, glass
transition takes place at T g = 224 K with Dcp = 0.131 J g-1 K-1 on
heating, Fig. 2b, and at T g = 219 K with Dcp = -0.117 J g-1 K-1 on
cooling.
An interesting phenomenon was observed during the DSC
measurements of the compounds formed at R = 0.5, stoichiomet- Fig. 2 Low temperature DSC curves of (a) [C1 C4 Im]Hf2 Cl9 and (b)
rically [C1 C4 Im][MCl5 ]. Both products appeared to consist of “wet [C1 C4 Im]Zr2 Cl9 on heating (heating rate 5 K min-1 ).
crystals”, and on cooling, glass transitions were found of around
225 K, similar to the values found for [C1 C4 Im][M2 Cl9 ]. For both runs produced different DSC profiles with endothermic peaks
metals, an exothermic peak appeared at around 340 K on heating, present at around 360 K and 380 K for Zr and Hf derivatives,
indicating the occurrence of a reaction in the system before a large respectively. However no T g was detected on further DSC analyses
endothermic peak due to melting at around 380 K. Subsequent of the same products. Removing the products from the system, it
1380 | Dalton Trans., 2010, 39, 1379–1388 This journal is © The Royal Society of Chemistry 2010
became clear that a reaction had occurred as the products were for Zr. In the case of Hf only the band [3(C1 C4 Im)MCl6 )]+ at m/z =
coloured solids, (pale green Hf, and red Zr). Deliberate formation 808.7 was present.
of this red Zr product by heating first to 473 K for 30 min gave DSC Negatively charged clusters due to the presence of Cl-
profiles with distinct endothermic peaks at 351 K and 374 K. One and Mx Cly - anions appear in the ESI- spectra. For R = 0.33,
hypothesis is that at room temperature there is formation of a the isotopic patterns corresponding to MCl5 - (m/z = 266.9 (Zr)
mixture of [C1 C4 Im][M2 Cl9 ] (liquid) and [C1 C4 Im]2 [MCl6 ] (solid), and 356.96 (Hf)) and the cluster [5(C1 C4 Im)3 (HfCl6 )]- , m/z =
the “kinetic products” as wet crystals, which on heating to 340 K 1867 were present. For R = 0.5 only the isotopic patterns
undergo a partial comproportionation reaction to give a eutectic corresponding to [MCl5 ]- {(m/z = 266.9 (Zr) and 356.9 (Hf)}
mixture, possibly containing M2 Cl10 2- anions already reported.35,36 were observed, Fig. 4. These data for R = 0.5 agree with the
DSC results showed firstly a variation in the melting point of structure [C1 C4 Im][MCl5 ] and not [C1 C4 Im]2 [M2 Cl10 ], as previ-
the salts produced, that was almost identical in the case of Hf ously reported.35,36
and Zr. Also interestingly, the complexes [C1 C4 Im][M2 Cl9 ] at R = For R = 0.67, as well as the isotopic pattern corresponding to
0.67 were still liquid at sub zero temperatures. The appearance [MCl5 ]- (m/z = 266.9 (Zr) and 356.9 (Hf), the isotopic pattern
of the DSC profiles themselves indicated that pure complexes corresponding to [M2 Cl9 ]- m/z = 500.3 for Zr, and m/z = 676.5
[C1 C4 Im]2 [MCl6 ], were achieved in the case of R = 0.33, as for Hf, and the cluster corresponding to [C1 C4 Im][Zr2 Cl9 ] at
these gave the sharpest most precise peak for the phase change. 1141.0 were apparent, Fig. 5. These results are consistent with
For R = 0.5, the DSC data would support the formation of findings by FTICR-MS, IR, and Raman spectra proving that
[M2 Cl10 ][C1 C4 Im]2 during the acquisition. [(C4 C4 ImCl)2(TiCl4 )] contained a large amount of [Ti2 Cl9 ]- ions
and a small amount of [TiCl6 ]2- ions.33
ESI mass spectrometry

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NMR experiments
Electrospray ionisation mass spectrometry is used to investigate
the nature of ILs in both the gas and solution phase and to The cation [C1 C4 Im]+ can be used as a probe to study the nature of
determine the nature of the ionic species present within.37-39 the ionic liquid. For this purpose, solutions of the different ionic
In the positive-ion mode mass spectra of the ionic liquids studied liquids in the same solvent (CD3 CN) and at the same concentration
at concentrations of ~10-6 M in acetonitrile, for all ionic liquids, and temperature (0.1 mol L-1 , 278 K), were analysed by 1 H, 13 C
the peak at m/z = 139.1 corresponding to the [C1 C4 Im]+ ion is NMR. Also, solid state 1 H, 13 C, NMR analyses have been run
present. The peak of the ion [2(C1 C4 Im)Cl]+ at m/z ~ 313, which on neat derivatives. The assignment of the nuclei is depicted in
decreased when R increased, was absent in each case when R = Scheme 2.
0.67. Larger clusters of [n(C1 C4 Im)(n-1)Cl]+ were not observed.
When R = 0.33 larger metal containing clusters were observed as
follows : [3(C1 C4 Im) MCl6 ]+ and m/z = 720.7 for Zr, and m/z =
808.7 for Hf, Fig. 3. At R = 0.5 clusters of [2(C1 C4 Im)MCl5 ]+ at
544.5 and 693.8 were observed for Zr and Hf, respectively. For R =
0.67 clusters of [2(C1 C4 Im)MCl5 ]+ at 544.5, [3(C1 C4 Im) MCl6 ]+ at
720.7 (major) and of [2(C1 C4 Im)M2 Cl9 )]+ at 776.1 were observed Scheme 2 Assignments of the C and H in the Imidazolium cation.
Fig. 3 (a) Full ESI+ mass spectra of products for R = 0.33 [C1 C4 Im]2 [HfCl6 ] (upper) and [C1 C4 Im]2 [ZrCl6 ] (lower), (b) zoom on the [(C1 C4 Im)3 MCl6 ]+
region showing isotopic peaks, (c) theoretical simulation of [C1 C4 Im]3 [MCl6 ]+ isotopic peaks for comparison.
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Fig. 4 (a) Zoom ESI- mass spectra of products for R = 0.5; Hf (upper) and Zr (lower), in [MCl5 ]- region showing isotopic peaks, (b) theoretical
simulation of [MCl5 ]- isotopic peaks for comparison.
Fig. 5 (a) Full ESI-mass spectra of R = 0.67 i.e. [C1 C4 Im][Hf2 Cl9 ] (upper) and [C1 C4 Im][Zr2 Cl9 ] (lower), (b) zoom on the [M2 Cl9 ]- region showing
isotopic peaks, (c) theoretical simulation of [M2 Cl9 ]- isotopic peaks for comparison.
1 13
H solution NMR C solution NMR
In 1 H NMR spectra of [C1 C4 Im]+ , the chemical shift of C2 – Besides the chemical shift of carbon C 2 (dC 2 ) which shifts towards
H proton (d H2 ) as well as ethylenic hydrogens C4 –H (d H 4 ) and high field with increasing R, Fig. 6c, the evolution of the 13 C NMR
C5 –H (d H5 ), although less markedly, exhibit a monotonous spectra is not significant (Dd < 0.1, Experimental part).
decrease with increasing R, Fig. 6a and 6b. This evolution could be The solution NMR analyses of both 1 H and 13 C of the
due to the decreasing hydrogen bond interactions between Cn –H imidazolium moiety, show clearly a linear displacement of chem-
and the anion as R increases. ical shifts with increasing MCl4 concentration. The addition
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Fig. 6 (Upper) Variation of the chemical shift in 1 H NMR (CD3 CN, 298 K, 0.1 mol L-1 , d ppm) of (a) d H 2 as a function of R (b) d H 4 and d H 5 as a
function of R. (Lower) Variation of the chemical shift of d C 2 in (c) 13 C solution NMR (CD3 CN, 0.1 mol L-1 , d ppm). (d) 13 C Solid state NMR, as a
function of R.
Table 1 Evolution of the chemical shift d C 2 –H in 1 H solution NMR and and R unlike for dC 2 , which is shifted monotonously towards
of the melting point for the ratios 0.33, 0.5 and 0.67 high field with increasing R, Fig. 6d. NMR analysis performed
in neat IL can reveal information, on the internal structure and
TiCl4 m.p. or Zr Cl4 m.p. or Hf Cl4 m.p. or AlCl3 m.p or
T g /K (d C 2 –H T g /K (d C 2 –H T g /K (d C 2 –H T g /K (d C 2 –H ionic association of these media. It could be proposed that the
R ppm)33 ppm)a ppm)a ppm)40,41 C2 H–anion H-bond is thus a significant factor in the tuning of the
physical properties of the resulting salt, Table 2.
0.33 377.96 (n.d) 363 (8.68) 391 (8.74) 213 (6.72)
0.5 337.5 (n.d) ~ 357 (8.49) ~ 370 (8.52) (6.5)
0.67 233.65 (n.d) 228 (8.40) 228 (8.40) 177 (6.2.5)
35
Cl liquid NMR (variable temperature)
a
This work.
In the 35 Cl NMR spectra of [C1 C4 Im]2 [HfCl6 ], and [C1 C4 Im]2 -
of MCl4 clearly has an effect on the electron density of the [ZrCl6 ], at 398 K, there is only one broad peak centred at 300 ppm,
ring. Ionic interactions in the MCl4 : ImCl system led to the which persists upon cooling to 378 K.
formation of hydrogen-bonded aggregates of anions and cations, The variable temperature 35 Cl solution NMR (CD3 CN) spectra
mainly through a C2 –H–anion interaction. The nature and extent [C1 C4 Im] Zr2 Cl9 showed two peaks at 450 and 350 ppm in a ratio of
of these depend on the susceptibility of the anion population around 1 : 2 which became sharper but did not shift when the tem-
towards hydrogen bond formation with Im+ . In general, the perature varied from 278 to 333 K. Similarly for [C1 C4 Im] Hf2 Cl9 ,
stronger C2 –H–anion hydrogen-bond induced, the more d C2 – peaks at 350 and 300 ppm are observed although the smaller is a
H is shifted to lower field, and the higher the melting point, shoulder possibly due to their proximity, Fig. 7. In the literature,
Table 1. the anion [M2 Cl9 ]- in complexes [M2 Cl9 ]- [C]+ M = Zr, Hf presents
the same structure of Cl3 M(m2 -Cl3 )MCl3 , i.e. six terminal chloride
13
C solid state NMR of IL in pure form at 298 K atoms and three bridging chloride atoms.42-45 Consequently, by
analogy with the structure of published [M2 Cl9 ]- [C]+ , the peaks at
In the 13 C solid state NMR (of neat IL), when the R value is 350 ppm (Hf) and 450 ppm (Zr) were assigned to the three bridging
increased all peaks are clearly affected, Table 2, particularly d C7 , chloride atoms and the peak at 300 ppm (Hf) and 350 ppm (Zr) to
d C 8 and d C10 , which are eventually completely replaced by three the six terminal chloride atoms. The 35 Cl NMR and ESI- findings
new peaks. However, there is no clear trend between their d values are consistent regarding the structure of these anions.
Table 2 13 C Solid-state NMR of neat compounds obtained by reaction of MCl4 with [C1 C4 Im][Cl] in ratios R = nMCl4 /nMCl4 + n[C1C4IM][Cl] equal to 0, 0.33,
0.5 and 0.67
Compound d C 2 (Dd) d C 4,5 d C7 d C6 d C8 d C9 d C 10
[C1 C4 Im]Cl 137.89 125.23 48.34 38.57 35.70 20.17 12.96

(0) 124.28
[C1 C4 Im]2 [ZrCl6 ], 136.31 124.19 49.90 38.10 31.91 19.28 15.09
(-1.58) 122.71 36.86 13.36
[C1 C4 Im]2 Zr2 Cl10 135.82 124.46 49.68 39.11 32.50 20.08 13.40
(-2.07) 123.15 37.52 10.83
[C1 C4 Im] Zr2 Cl9 134.76 124.84 51.05 37.50 32.18 19.58 14.03
(-3.13) 123.39
[C1 C4 Im]2 [HfCl6 ], 136.56 124.46 50.72 38.10 32.66 20.04 15.09
(-1.33) 123.47 36.62 13.36
[C1 C4 Im]2 Hf2 Cl10 135.59 123.22 49.73 39.34 32.41 20.04 13.36
(-2.30) 10.88
[C1 C4 Im] Hf2 Cl9 134.52 124.61 51.03 37.16 32.20 19.57 13.87
(-3.37) 123.37
tel-00708600, version 1 - 15 Jun 2012
Fig. 7 Variable temperature NMR spectra; (a) 35 Cl of [C1 C4 Im][Hf2 Cl9 ], (b) 35 Cl of [C1 C4 Im][Zr2 Cl9 ].
Thermal dissociation by 35 Cl and 91 Zr solid NMR (high M’2 [ZrCl6 ] → 2M’Cl + ZrCl4 .
temperature) of [C1 C4 Im]2 HfCl6 , and [C1 C4 Im]2 ZrCl6
In the case of 1-butyl-2,3-dimethylimidazolium trichlorozincate Due to the presence of a strong hydrogen bond B–H ◊ ◊ ◊ Cl the
[C1 C1 C4 Im][ZnCl3 ] and 1-butyl-3-methylimidazolium trichloro- thermal dissociation, with BHCl, is total only in the presence of
zincate [C1 C4 Im][ZnCl3 ], the results of variable temperature 35 Cl oxygen affording ZrO2 instead of ZrCl4 which is economically
and 13 C NMR analyses indicated that the species are dissociated unavailable for the Zr/Hf separation process.
to give ImCl and ZnCl2 , at temperatures superior to 373 K and The thermogravimetric analysis (TGA) of [C1 C4 Im]2 [ZrCl6 ], and
338 K, respectively.46 The reverse process was observed on cooling. [C1 C4 Im]2 [HfCl6 ], indicated also that the weight losses began at
This dissociation could be used for the recovery and/or separation 528 K and 538 K, respectively, instead of 493 K for [C1 C4 Im]Cl.
of a metal chloride from a mixture. Such dissociation in the This shows firstly, the presence of the chlorometallate increases
case of zirconium and/or hafnium chloride would be of crucial significantly the thermal stability, and secondly no significant
interest for their separation which is still an economic challenge.34 difference is apparent between the Zr and Hf compounds.
Furthermore, in the literature MCl4 compounds are described as Due to these findings, 35 Cl and 91 Zr solid NMR spectra could
typical Lewis acids that readily react with chloride ions to produce be run at high temperatures ranging from 513 K to 551 K,
the hexachlorometallate ion, either with alkali metals: Fig. 8. The spectra were recorded both with increasing and
decreasing temperature. For 35 Cl, the peak width decreases with
2M’Cl + ZrCl4 → M’2 [ZrCl6 ]47,48 temperature corresponding to a decrease in viscosity. A small
displacement combined with a decrease of the peak width is
or with bases such as pyridine or quinoline (B) in the presence of
observed at low temperature. This may be due to an increase of
HCl: 35
Cl mobility towards the C1 C4 Im cation. No such phenomenon
2B + 2HCl + ZrCl4 → (BH)2 [ZrCl6 ].49 is observed in the 91 Zr spectrum, whose peak remains sharp at all
the temperatures. Consequently, no dissociation was observed and
All these compounds undergo thermal dissociation at 622 K for so no decomposition occurred. This result for [C1 C4 Im]2 [ZrCl6 ],
KCl and above 522 K for (BHCl): could be explained by the presence of a close interaction between
liquids whose catalytic properties are currently under study. The
high temperature 35 Cl and 91 Zr solid state NMR experiments show
that there is no dissociation of [C1 C4 Im]2 MCl6 in [C1 C4 Im][Cl] and
MCl4 up to 551 K. This result could be explained by the presence
of a close interaction between the acidic ring protons and the
chlorine of the anion.
Experimental
All operations were performed in the strict absence of oxygen and
water under a purified argon atmosphere using glovebox (Jacomex
or MBraun) or vacuum-line techniques. Under argon, solvents
were distilled using the appropriate drying agents: pyridine
from CaH2 , acetonitrile and acetonitrile-d 3 (99% de deuterium)
from P2 O5 and stored over molecular sieves. 1-chlorobutane and
1,2-dimethylimidazole were obtained from Aldrich, and were
freshly distilled before use. 1-Butyl-3-methylimidazolium chloride
[C1 C4 Im][Cl] was synthesised as described in the literature.1
1
H and 13 C and 35 Cl liquid NMR
tel-00708600, version 1 - 15 Jun 2012
Solution NMR spectra were recorded on a Bruker Avance

300 MHz spectrometer for 1 H and 13 C and a DRX 500 MHz
spectrometer for 35 Cl. Chemical shifts were measured relative to
SiMe4 as internal standard for 1 H and 13 C and relative to external
HCl (0.1 mol L-1 in H2 O) for 35 Cl. The sample for 35 Cl NMR
was prepared as follows : the sample was introduced in an NMR
tube (5 mm) in a glovebox. Then, the NMR tube was put inside
a Schlenk tube, which was heated, under argon, until compounds
were liquefied and put under vacuum for 1 h. Then, a capillary of
DMSO-d 6 was introduced under argon into the molten solid.
1
H and 13 C solid NMR
Solid state NMR spectra were recorded on a Bruker DSX-300

spectrometer equipped with a standard 4 mm double-bearing
probe head and operating at 75.47, and 300.18 MHz for 13 C, and
1
H, respectively. 13 C NMR spectra were recorded as follows : 30◦
pulse on 13 C nuclei, and acquisition under a 80 kHz decoupling
field on protons, with 1 s recycle delay and 5 kHz spinning speed
unless otherwise specified.
Fig. 8 Variable temperature NMR spectra; (a) 35 Cl of [C1 C4 Im]2 HfCl6 , 35
(b) 35 Cl of [C1 C4 Im]2 ZrCl6 , (c) 91 Zr of [C1 C4 Im]2 ZrCl6 . Cl, 91 Zr high temperature NMR
The High Temperature NMR (HT NMR) spectra were recorded

the acidic ring protons and the chlorine of the anion indicated by
using a Bruker Avance WB 400 MHz spectrometer, operating
the crystallographic data.22
at 9.40 T. In situ HT NMR spectra were obtained by using
the CO2 laser heating system developed at CRMHT-CNRS in
Conclusion Orléans (France) and previously described.50,51 To prevent sample
contamination by air, the samples were put in a BN (HIP grade)
1-Butyl-3-methylimidazolium chlorometallates were prepared by
crucible inside a glovebox under argon. The HT NMR spectra
the combination of MCl4 (M = Zr, Hf) with [C1 C4 Im][Cl]. The
were acquired using a single pulse sequence. For 35 Cl and 91 Zr,
molar percentage of MCl4 was varied as follows; R = nMCl4 /nMCl4 +
the parameters were a recycle delay of 0.3 s, p/2 pulses of 35 ms
n[C1C4IM][Cl] equal to 0, 0.1, 0.2, 0.33, 0.5, 0.67. Pure compounds
with 1024 accumulations. The chemical shifts were referred to
[C1 C4 Im]2 [MCl6 ], [C1 C4 Im][M2 Cl9 ] have been fully characterised
NaCl 1 mol L-1 solution for 35 Cl and to a saturated solution of
by DSC, 1 H and 13 C solid state and solution NMR spectroscopy,
(h5 -C5 H5 )2 ZrCl2 in CH2 Cl2 for 91 Zr.
and ESI mass spectrometry. The primary anions of the MCl4 -
based ILs were [MCl5 ], [MCl6 ] and [M2 Cl9 ], whose abundances DSC procedure52
varied with R. The variable temperature 35 Cl solution NMR
spectra [C1 C4 Im][M2 Cl9 ] allowed us to identify the bridging and Compounds were investigated with a Setaram DSC 121 differen-
terminal chlorine atoms. [C1 C4 Im][M2 Cl9 ] constitute new ionic tial scanning calorimeter. Experimental samples (30–50 mg) were
contained in vacuum-sealed PyrexTM cells (7 mm diameter and necessary with use of a heat gun, in order to obtain a homogenous
15 mm long). In order to avoid compound decomposition during solution. The products are left stirring for 2 h and then cooled
sealing under reduced pressure of argon, the ampoule containing down to room temperature. A solid is obtained for R = 0.2, 0.33,
the compound was cooled down to liquid nitrogen temperature a semi-solid for R = 0.5, and liquids obtained for R = 0.1, 0.7.
just before sealing. The side walls and bottom of the ampoules were Example of the synthesis of 1-butyl-3-methylimidazolium zirco-
grounded in order to make these cells fit snugly into the heat flow nium pentachloride: {[C1 C4 Im][ZrCl5 ], with R = 0.5}: Anhydrous
detector. This consists of two thermopiles, connected in electrical zirconium tetrachloride (0.667 g, 2.86 mmol) was mixed under
opposition, accommodating both the previous experimental cell argon with solid 1-butyl-3-methylimidazolium chloride (0.5 g,
with the sample and another empty and identical cell, which acts as 2.86 mmol). The mixture was heated to 70 ◦ C and stirred over
a reference. This experimental DSC set up is characterised both by 2 h until a homogenous mixture formed.
1
a high sensitivity and an excellent integration of the thermal heat H NMR (CD3 CN, d) : 8.49 (1H, s, C2 H), 7.38 and 7.34 (2H,
flow since the sensing thermocouples in each thermopile are evenly d, C4,5 H), 4.20 (2H, t, C7 H 2 ), 3.83 (3H, s, C6 H 3 ), 1.80 (2H,
distributed all over the cell surface. Experiments were conducted qn, C8 H 2 ), 1.31 (2H, sx, C9 H 2 ), 0.95 (3H, t, C10 H 3 ).13 C NMR
at heating and cooling rates ranging up to 5 K min-1 . (CD3 CN, d) : 136.83 (s, C2 ), 124.59 and 123.21 (d, C4,5 ), 50.30
As the differential scanning calorimeter works in a wide temper- (s, C7 ), 36.98 (s, C6 ), 32.56 (s, C8 ), 19.91 (s, C9 ), 13.65 (s, C10 ).13 C
ature range, knowledge of the calorimeter constant dependence Solid-state NMR (d) : 135.82 (C2 ), 124.46 and 123.15 (C4,5 ), 49.68
on temperature is crucial in measurements with this apparatus. (C7 ), 39.11 and 37.52 (C6 ), 32.50 (C8 ), 20.08 and 19.02 (C9 ),
Such a dependence for Setaram DSC 121 was determined during 13.47 and 10.83 (C10 ). ESI+ : 139.1 [C1 C4 Im+ ], 312.8 [2(C1 C4 Im+ )
calorimeter calibration by the “ Joule effect”. This calibration Cl- ], 544.5 [2(C1 C4 Im+ )ZrCl5 - ], 721.0 [3(C1 C4 Im+ ) ZrCl6 2- ], 1302.8
was carried out at defined temperatures by the so-called “step [5(C1 C4 Im+ ) 2ZrCl6 2- ] ESI- : 266.9 [ZrCl5 - ]
method” (DT = 5 K) over the entire temperature range of the
tel-00708600, version 1 - 15 Jun 2012
calorimeter work. As a result the calibration curve, i.e. calorimeter [C1 C4 Im+ ][Cl- ] (R = 0). 1 H NMR (CD3 CN, d) : 9.70 (1H, s,
constant dependence on temperature, K(mV mW-1 ) = f (T), was C2 H), 7.49 and 7.46 (2H, d, C4,5 H), 4.20 (2H, t, C7 H 2 ), 3.88 (3H, s,
obtained. This dependence was automatically used during data C6 H 3 ), 1.81 (2H, qn, C8 H 2 ), 1.30 (2H, sx, C9 H 2 ), 0.91 (3H, t,
treatment by the original Setaram software. The measurement C10 H 3 ). 13 C NMR (CD3 CN, d) : 138.35 (s, C2 ), 124.38 and 123.13
of sample temperature was performed through a platinum probe (d, C4,5 ), 49.80 (s, C7 ), 36.56 (s, C6 ), 32.58 (s, C8 ), 19.83 (s, C9 ), 13.63
located in the calorimetric block. The fusion of standard materials (s, C10 ). 13 C Solid-state NMR (d) : 137.89 (C2 ), 125.23 and 124.28
was studied at various scanning rates and temperature correction (C4,5 ), 48.34 (C7 ), 38.57 (C6 ), 35.70 (C8 ), 20.17 (C9 ), 12.96 (C10 ).
coefficients were determined and introduced into the calorimeter M = Zr R = 0.1 ; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); ZrCl4
software. The maximum relative error of enthalpy of phase (7.40 ¥ 10-2 g, 3.17 ¥ 10-4 mol) 1 H NMR (CD3 CN, d) : 9.52
transition determination did not exceed 1%. It was checked by (1H, s, C2 H), 7.47 and 7.43 (2H, d, C4,5 H), 4.19 (2H, t, C7 H 2 ),
measurements of temperature and enthalpy of phase transitions 3.88 (3H, s, C6 H 3 ), 1.81 (2H, qn, C8 H 2 ), 1.30 (2H, sx, C9 H 2 ), 0.91
of standard substances. Results obtained (differences in fusion (3H, t, C10 H 3 ). 13 C NMR (CD3 CN, d) : 138.16 (s, C2 ), 124.41
temperatures less than 1 K, differences in enthalpies of fusion less and 123.10 (d, C4,5 ), 49.98 (s, C7 ), 36.67 (s, C6 ), 32.60 (s, C8 ),
than 0.5%) confirmed the correct working of the calorimeter. 19.88 (s, C9 ), 13.63 (s, C10 ). 13 C Solid-state NMR (d) : 138.06 (C2 ),
125.45 and 124.21 (C4,5 ), 48.49 (C7 ), 38.60 (C6 ), 35.88 (C8 ), 20.04
Mass spectrometry (C9 ), 13.36 (C10 ). ESI+ : 139.1 (C1 C4 Im+ ), 312.8 ([2C1 C4 Im,35 Cl]+ )
ESI- : 384.8 ([2C1 C4 Im+ ,335 Cl- ]), 556.8 ([3C1 C4 Im+ ,435 Cl- ]), 734.8
Mass spectra were acquired on a ThermoFinnigan LCQ Advan- ([4C1 C4 Im+ ,535 Cl- ])
tage ion trap instrument, detecting positive (+) and negative (-) R = 0.2 ; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); ZrCl4 (0.167 g, 7.15 ¥
ions in the ESI mode. Samples (1 to 10 mg ml-1 in acetonitrile) were 10-4 mol) 1 H NMR (CD3 CN, d) : 9.15 (1H, s, C2 H), 7.42 and 7.39
infused directly into the source (5 ml min-1 ) using a syringe pump. (2H, d, C4,5 H), 4.20 (2H, t, C7 H 2 ), 3.87 (3H, s, C6 H 3 ), 1.81 (2H,
The following source parameters were applied: spray voltage qn, C8 H 2 ), 1.30 (2H, sx, C9 H 2 ), 0.92 (3H, t, C10 H 3 ). 13 C NMR
3.0–3.5 kV, nitrogen sheath gas flow 5–20 arbitrary units. The (CD3 CN, d) : 137.81 (s, C2 ), 124.42 and 123.09 (d, C4,5 ), 49.99
heated capillary was held at 473 K. MS spectra were obtained by (s, C7 ), 36.74 (s, C6 ), 32.59 (s, C8 ), 19.85 (s, C9 ), 13.62 (s, C10 ).
13
applying a relative collision energy of 25 to 40% of the instrumental C Solid-state NMR (d) : 137.97 (C2 ), 125.16 and 124.18 (C4,5 ),
maximum. 50.75 and 48.49 (C7 ), 38.59 (C6 ), 35.68 (C8 ), 20.35 (C9 ), 13.95
(C10 ). ESI+ : 139.1 (C1 C4 Im+ ), 312.8 ([2C1 C4 Im,35 Cl]+ ) ESI- : 268.8
Preparation of ionic liquid (ZrCl5 - ), 384.8 ([2C1 C4 Im+ ,335 Cl- ]), 556.8 ([3C1 C4 Im+ ,435 Cl- ]),
734.8 ([4C1 C4 Im+ ,535 Cl- ]).
Under argon in glovebox, the solid reactants are weighed and R = 0.33 ; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); ZrCl4 (0.333 g, 1.43 ¥
mixed together thoroughly using a mortar and pestle. For each 10-3 mol) 1 H NMR (CD3 CN, d) : 8.68 (1H, s, C2 H), 7.38 and 7.36
experiment, 0.5 ± 0.005 g (2.86 ¥ 10-3 mol) of the ionic liquid (2H, d, C4,5 H), 4.20 (2H, t, C7 H 2 ), 3.86 (3H, s, C6 H 3 ), 1.81 (2H,
C1 C4 ImCl (relative molecular mass 174.7 g mol-1 , white solid at qn, C8 H 2 ), 1.32 (2H, sx, C9 H 2 ), 0.94 (3H, t, C10 H 3 ). 13 C NMR
room temperature) is weighed into each tube and the according (CD3 CN, d) : 137.20 (s, C2 ), 124.54 and 123.13 (d, C4,5 ), 50.24
amounts of MCl4 are added. (s, C7 ), 36.97 (s, C6 ), 32.66 (s, C8 ), 19.92 (s, C9 ), 13.65 (s, C10 ). 13 C
This is then heated to 343 K, (m.p. C1 C4 ImCl = 339 K), under Solid-state NMR (d) : 136.31 (C2 ), 124.19 and 122.71 (C4,5 ), 49.97
constant stirring. This produces a homogenous solution except (C7 ), 38.10 and 36.86 (C6 ), 31.91 (C8 ), 19.28 (C9 ), 15.09, 13.36 and
for in the cases of R = 0.33 and R = 0.5, where extra heating is 11.63 (C10 ). ESI+ : 139.1 [C1 C4 Im+ ], 313.0 [2(C1 C4 Im+ ) Cl- ], 720.7
[3(C1 C4 Im+ ) ZrCl6 2- ], 1302.8 [5(C1 C4 Im+ ) 2ZrCl6 2- ] ESI- : 266.9 13
C Solid-state NMR (d) : 134.52 (C2 ), 124.61 and 123.37 (C4,5 ),
[ZrCl5 - ] 51.03 (C7 ), 37.16 (C6 ), 32.20 (C8 ), 19.57 (C9 ), 13.87 (C10 ). ESI+ :
R = 0.67; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); ZrCl4 (1.56 g, 139.1 [C1 C4 Im+ ], 808.7 [3(C1 C4 Im+ ) HfCl6 2- ] ESI- : 356.9 [HfCl5 - ],
6.67 mmol) 1 H NMR (CD3 CN, d) : 8.40 (1H, s, C2 H), 7.35 and 676.5 [Hf2 Cl9 - ]
7.31 (2H, d, C4,5 H), 4.12 (2H, t, C7 H 2 ), 3.80 (3H, s, C6 H 3 ), 1.78
(2H, qn, C8 H 2 ), 1.27 (2H, sx, C9 H 2 ), 0.88 (3H, t, C10 H 3 ). 13 C NMR
(CD3 CN, d) : 136.61 (s, C2 ), 124.57 and 123.20 (d, C4,5 ), 50.31 (s,
Acknowledgements
C7 ), 37.01 (s, C6 ), 32.49 (s, C8 ), 19.90 (s, C9 ), 13.69(s, C10 ). 13 C We would like to thank Areva Cezus for financing this work, Anne
Solid-state NMR (d) : 134.76 (C2 ), 124.84 and 123.39 (C4,5 ), 51.05 Baudouin for solid state NMR and also undergraduate students
(C7 ), 37.50 (C6 ), 32.18 (C8 ), 19.58 (C9 ), 14.03 (C10 ). ESI+ : 139.1 Céline Chong, Thibault Alphazan and Sandra Garcia for their
[C1 C4 Im+ ], 544.5 [2(C1 C4 Im+ )ZrCl4 - ], 720.7 [3(C1 C4 Im+ )ZrCl6 2- ], participation.
776.1 [2(C1 C4 Im+ )Zr2 Cl9 - ]ESI- : 266.9 [ZrCl5 - ], 500.3 [Zr2 Cl9 - ],
1141.0 [C1 C4 Im+ 2Zr2 Cl9 - ]
M = Hf R = 0.1; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); HfCl4 (0.102 g, Notes and references
3.17 ¥ 10-4 mol) 1 H NMR (CD3 CN, d): 9.44 (1H, s, C2 H), 7.46 1 P. Wasserscheid and T. Welton, Ionic Liquids in Synthesis, Wiley-VCH,
and 7.43 (2H, d, C4,5 H), 4.19 (2H, t, C7 H 2 ), 3.87 (3H, s, C6 H 3 ), Weinheim, 2003.
1.78 (2H, qn, C8 H 2 ), 1.32 (2H, sx, C9 H 2 ), 0.91 (3H, t, C10 H 3 ). 13 C 2 A. P. Abbott, G. Capper, D. L. Davies and R. K. Rasheed, Chem.–
Eur. J., 2004, 10, 3769–3774.
NMR (CD3 CN, d) : 138.10 (s, C2 ), 124.37 and 123.07 (d, C4,5 ), 3 R. T. Carlin and R. A. Osteryoung, J. Mol. Catal., 1990, 63, 125–
49.89 (s, C7 ), 36.64 (s, C6 ), 32.57 (s, C8 ), 19.86 (s, C9 ), 13.60 (s, C10 ). 129.
13
C Solid-state NMR (d) : 137.82 (C2 ), 125.44 and 124.21 (C4,5 ), 4 Y. Chauvin, S. Einloft and B. H. Olivier, Ind. Eng. Chem. Res., 1995,
34, 1149–1155.
48.50 (C7 ), 38.84 (C6 ), 35.88 (C8 ), 20.28 (C9 ), 13.11 (C10 ). ESI+ :
tel-00708600, version 1 - 15 Jun 2012
5 K. Yoo, V. V. Namboodiri, R. S. Varma and P. G. Smirniotis, J. Catal.,

139.1 [C1 C4 Im+ ], 312.8 [2(C1 C4 Im+ ) Cl- ] ESI- : 2004, 222, 511–519.
R = 0.2; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); HfCl4 (0.229 g, 7.15 ¥ 6 Y. Gu, F. Shi and Y. Deng, J. Mol. Catal. A: Chem., 2004, 212, 71–
10-4 mol) 1 H NMR (CD3 CN, d) : 9.35 (1H, s, C2 H), 7.47 and 7.43 75.
7 R. A. Osteryoung, Molten Salt Chemistry, Reidel Publishing,
(2H, d, C4,5 H), 4.18 (2H, t, C7 H 2 ), 3.91 (3H, s, C6 H 3 ), 1.81 (2H, Dordrecht, Holland, 1987.
qn, C8 H 2 ), 1.28 (2H, sx, C9 H 2 ), 0.90 (3H, t, C10 H 3 ). 13 C NMR 8 R. T. Carlin and R. A. Osteryoung, J. Electroanal. Chem., 1988, 252,
(CD3 CN, d) : 137.77 (s, C2 ), 124.38 and 123.06 (d, C4,5 ), 49.92 (s, 81.
C7 ), 36.71 (s, C6 ), 32.56 (s, C8 ), 19.80 (s, C9 ), 13.59 (s, C10 ). 13 C 9 A. A. Fannin, L. A. King, J. A. Levisky and J. S. Wilkes, J. Phys. Chem.,
1984, 88, 2609–2614.
Solid-state NMR (d) : 138.06 (C2 ), 125.69 and 124.21 (C4,5 ), 49.98 10 C. Woodcock and D. F. Shriver, Inorg. Chem., 1986, 25, 2137.
and 48.50 (C7 ), 38.84 (C6 ), 35.88 (C8 ), 20.29 (C9 ), 13.11 (C10 ). ESI+ : 11 J. T. A. Zawodzinski and R. A. Osteryoung, Inorg. Chem., 1989, 28,
139.1 (C1 C4 Im+ ), 312.8 ([2 C1 C4 Im,35 Cl]+ ) ESI- : 354.9 [HfCl5 - ] 1710.
12 Y. Chauvin, F. Di Marco-Van Tiggelen and H. Olivier, J. Chem. Soc.,
R = 0.33; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); HfCl4 (0.458 g, Dalton Trans., 1993, 1009–1011.
1.43 mmol) 1 H NMR (CD3 CN, d) : 8.74 (1H, s, C2 H), 7.40 and 13 C. A. Angell and P. D. Bennett, J. Am. Chem. Soc., 1982, 104, 6304.
7.37 (2H, d, C4,5 H), 4.17 (2H, t, C7 H 2 ), 3.87 (3H, s, C6 H 3 ), 1.80 14 B. Gilbert, Y. Chauvin and I. Guibard, Vib. Spectrosc., 1991, 1, 299–
(2H, qn, C8 H 2 ), 1.30 (2H, sx, C9 H 2 ), 0.91 (3H, t, C10 H 3 ). 13 C 304.
15 Y. Chauvin, B. H. Olivier, C. Wyrvalski, L. C. Simon and R. F. de
NMR (CD3 CN, d) : 137.23 (s, C2 ), 124.51 and 123.12 (d, C4,5 ), Souza, J. Catal., 1997, 165, 275–278.
50.19 (s, C7 ), 36.96 (s, C6 ), 32.65 (s, C8 ), 19.89 (s, C9 ), 13.64 (s, C10 ). 16 X. Liu, L. Xiao, H. Wu, Z. Li, J. Chen and C. Xia, Catal. Commun.,
13
C Solid-state NMR (d) : 136.56 (C2 ), 124.46 and 123.47 (C4,5 ), 2009, 10, 424–427.
17 J. Zhang, C. Hunang, B. Chen, P. Ren and M. Pu, J. Catal., 2007, 249,
50.72 (C7 ), 38.10 and 36.62 (C6 ), 32.66 (C8 ), 20.04 (C9 ), 15.09 and
261–268.
13.36 (C10 ). ESI+ : 139.1 [C1 C4 Im+ ], 312.9 [2(C1 C4 Im+ ) Cl- ], 808.7 18 X. Liang, G. Gong, H. Wu and J. Yang, Fuel, 2009, 88, 613–616.
[3(C1 C4 Im+ ) HfCl6 2- ], 1447.6 [5(C1 C4 Im+) 2HfCl6 2- )] ESI- : 356.9 19 Q.-G. Zhang and Y. Wei, J. Chem. Thermodyn., 2008, 40, 640–644.
[HfCl5 - ], 1867.4 [5(C1 C4 Im+ ) 3HfCl6 2- ] 20 X.-w. Zhang and Q.-h. Ai, Huaxue Shiji, 2008, 30, 121–124.
21 M. S. Sitze, E. R. Schreiter, E. V. Patterson and R. G. Freeman, Inorg.
R = 0.5; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); HfCl4 (0.916 g, Chem., 2001, 40, 2298–2304.
2.86 mmol) 1 H NMR (CD3 CN, d) : 8.52 (1H, s, C2 H), 7.36 and 22 C. Zhong, T. Sasaki, A. Jimbo-Kobayashi, E. Fujiwara, A. Kobayashi,
7.31 (2H, d, C4,5 H), 4.14 (2H, t, C7 H 2 ), 3.81 (3H, s, C6 H 3 ), 1.80 M. Tada and Y. Iwasawa, Bull. Chem. Soc. Jpn., 2007, 80, 2365–2374.
(2H, qn, C8 H 2 ), 1.29 (2H, sx, C9 H 2 ), 0.90 (3H, t, C10 H 3 ). 13 C 23 X. Chen and Y. Peng, Catal. Lett., 2008, 122, 310–313.
24 A. P. Abbott, ChemPhysChem, 2004, 5, 1242–1246.
NMR (CD3 CN, d) : 136.97 (s, C2 ), 124.46 and 123.06 (d, C4,5 ), 25 D. Ballivet-Tkatchenko, M. Picquet, M. Solinas, G. Francio, P.
50.14 (s, C7 ), 36.92 (s, C6 ), 32.53 (s, C8 ), 19.80 (s, C9 ), 13.57 (s, Wasserscheid and W. Leitner, Green Chem., 2003, 5, 232–235.
C10 ). 13 C Solid-state NMR (d) : 135.59 (C2 ), 123.22 (C4,5 ), 49.73 26 T. J. Bell, A. P. Abbott, S. Handa and B. Stoddart, Abstracts of Papers,
231st ACS National Meeting, Atlanta, 2006.
(C7 ), 39.34 (C6 ), 32.41 (C8 ), 20.04 (C9 ), 13.36 and 10.88 (C10 ). 27 V. Lecocq, A. Graille, C. C. Santini, A. Baudouin, Y. Chauvin, J.-M.
ESI+ : 139.1 [C1 C4 Im+ ], 313.0 [2(C1 C4 Im+ ) Cl- ], 693.8[2(C1 C4 Im+ ) Basset, D. Bouchu and B. Fenet, New J. Chem., 2005, 29, 700–706.
HfCl5 - ], 809.0 [3(C1 C4 Im+ ) HfCl6 2- ], 1447.8 [5(C1 C4 Im+ ) 2HfCl6 2- ] 28 J. L. Anthony, J. F. Brennecke, J. D. Holbrey, E. J. Maginn, R. A.
ESI- : 356.9 [HfCl5 - ] Mantz, R. D. Rogers, P. C. Trulove, A. E. Visser and T. Welton, in
Ionic Liquids in Synthesis, Ed. P. Wasserscheid, T. Welton, Wiley-VCH,
R = 0.67; [C1 C4 Im][Cl] (0.5 g, 2.86 mmol); HfCl4 (2.13 g, Weinheim, 2003, pp. 41-55.
6.67 mmol) 1 H NMR (CD3 CN, d) : 8.40 (1H, s, C2 H), 7.33 and 29 G. D. Allen, M. C. Buzzeo, I. G. Davies, C. Villagran, C. Hardacre and
7.29 (2H, d, C4,5 H), 4.07(2H, t, C7 H 2 ), 3.78 (3H, s, C6 H 3 ), 1.75 R. G. Compton, J. Phys. Chem. B, 2004, 108, 16322–16327.
30 P. B. Hitchcock, K. R. Seddon and T. Welton, J. Chem. Soc., Dalton
(2H, qn, C8 H 2 ), 1.25 (2H, sx, C9 H 2 ), 0.84 (3H, t, C10 H 3 ). 13 C
Trans., 1993, 2639.
NMR (CD3 CN, d) : 136.21 (s, C2 ), 125.62 and 124.18 (d, C4,5 ), 31 M. Hasan, I. V. Kozhevnikov, M. Siddiqui, C. Femoni, A. Steiner and
49.91 (s, C7 ), 36.63 (s, C6 ), 32.10 (s, C8 ), 19.51 (s, C9 ), 13.32(s, C10 ). N. Winterton, Inorg. Chem., 2001, 40, 795–800.
32 P. B. Hitchcock, R. J. Lewis and T. Welton, Polyhedron, 1993, 12, 43 F. Musso, E. Solari, C. Floriani and K. Schenk, Organometallics, 1997,
2039. 16, 4889–4895.
33 L. Gao, L. Wang, T. Qi, J. Chu and J. Qua, J. Electrochem. Soc., 2009, 44 M. Schormann, S. Garratt, D. L. Hughes, J. C. Green and M.
156, 49–55. Bochmann, J. Am. Chem. Soc., 2002, 124, 11266–11267.
34 R. H. Nielsen, in Kirk Othmer Encyclopedia of Chemical Technology, 45 M. Schormann, S. Garratt and M. Bochmann, Organometallics, 2005,
Wiley, New York, 2004. 24, 1718–1724.
35 B. Neumueller and K. Dehnicke, Z. Anorg. Allg. Chem., 2004, 630, 46 C. C. Cassol, G. Ebeling, B. Ferrera and J. Dupont, Adv. Synth. Catal.,
2576–2578. 2006, 348, 243–248.
36 E. Robe, S. Maria, P. Richard and R. Poli, Eur. J. Inorg. Chem., 2007, 47 J. E. Drake and G. W. A. Fowles, J. Inorg. Nucl. Chem., 1961, 18, 136.
2434–2442. 48 P. Gelbman and A. D. Westland, J. Chem. Soc., Dalton Trans., 1975,
37 F. C. Gozzo, L. S. Santos, R. Augusti, C. S. Consorti, J. Dupont and 1598.
M. N. Eberlin, Chem.–Eur. J., 2004, 10, 6187–6193. 49 H. V. Thanh, L. Gruzdiewa, J. Rak and J. Blazejowski, Thermochim.
38 P. J. Dyson, I. Khalaila, S. Luettgen, J. S. McIndoe and D. Zhao, Chem. Acta, 1993, 230, 269–292.
Commun., 2004, (19), 2204–2205. 50 V. Lacassagne, C. Bessada, B. Ollivier, D. Massiot and J.-P. Coutures,
39 D. F. Kennedy and C. J. Drummond, J. Phys. Chem. B, 2009, 113, C. R. Acad. Sci. IIb, 1997, 325, 91–98.
5690–5693. 51 D. Massiot, C. Bessada, P. Echegut, J. P. Coutures and F. Taullele, Solid
40 C. Scordilis-Kelley, K. D. Robinson, K. A. Belmore, J. L. Atwood and State Ionics, 1990, 37, 223.
R. T. Carlin, J. Crystallogr. Spectrosc. Res., 1993, 23, 601–606. 52 (a) M. Gaune-Escard, Calorimetric methods, in Molten Salt Tech-
41 D. Bankmann and R. Giernoth, Prog. Nucl. Magn. Reson. Spectrosc., niques, Eds. R.J. Gale and D. G. Lovering, Vol. 4, Plenum Press, New
2007, 51, 63–90. York, pp. 151-192 (1991); (b) E. Ingier-Stocka, L. Rycerz, M. Berkani
42 F. Calderazzo, I. Ferri, G. Pampaloni and S. Troyanov, J. Organomet. and M. Gaune-Escard, J. Mol. Liq., 2009, 148, 40–44 and references
Chem., 1996, 518, 189–196. therein.
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TH2010 Campbell Paul

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N° d’ordre 212-2010 Année 2010

devant l’UNIVERSITE CLAUDE BERNARD - LYON 1

UTILISING THE SOLVATION PROPERTIES OF IONIC LIQUIDS IN THE

présentée et soutenue publiquement le jeudi 28 octobre 2010 devant la commission d’examen :

Président de l’Université M. le Professeur L. Collet

Vice-président du Conseil Scientifique M. le Professeur J-F. Mornex

Vice-président du Conseil d’Administration M. le Professeur G. Annat

Vice-président du Conseil des Etudes et de la Vie Universitaire M. le Professeur D. Simon

Secrétaire Général M. G. Gay

Faculté de Médecine Lyon Est – Claude Bernard Directeur : M. le Professeur J. Etienne

COMPOSANTES ET DEPARTEMENTS DE SCIENCES ET TECHNOLOGIE

Faculté des Sciences et Technologies Directeur : M. le Professeur F. Gieres

and for my Mum and Dad

s: singlet, d: doublet, t: triplet, q: quadruplet, quint: quintuplet, sext: sextuplet, m: multiplet

COD: 1,5-cyclooctadiene COT: 1,3,5-cyclooctatriene COA: cyclooctane

UTILISING THE SOLVATION PROPERTIES OF IONIC LIQUIDS IN THE SIZE-

UTILISATION DES PROPRIETES DE SOLVATATION DES LIQUIDES IONIQUES EN

Chapter 1 Ruthenium Nanoparticles 19

Chapter 2 Generation and Stabilisation of Transition Metal 51

Chapter 3 Imidazolium Ionic Liquids as Media for Homogeneous 105

Chapter 4 Nanoparticle Catalysis in Imidazolium Ionic Liquids 155

General Conclusion 187

Appendix 1 Characterisation of Nickel Nanoparticles by XPS 195

Appendix 2 Publications 199

Appendix 3 Separation of Hafnium from Zirconium in Ionic Liquids 235

9. T. Gutel, C. C. Santini, K. Philippot, A. Padua, K. Pelzer, B. Chaudret, Y. Chauvin and

Synthesis, Stabilisation &

1.1 Introduction .................................................................................................................................... 23

1.2 Syntheses ....................................................................................................................................... 24

1.2.1 RuNPs synthesised directly on supports .................................................................................... 24

1.2.2 Solvothermal synthesis .............................................................................................................. 25

1.2.3 Colloidal synthesis in organic solvents...................................................................................... 27

1.2.4 Aqueous Synthesis..................................................................................................................... 31

1.2.5 Synthesis in ionic liquids ........................................................................................................... 32

1.2.6 Glossary of RuNP syntheses...................................................................................................... 34

1.3 Catalytic properties ........................................................................................................................ 36

1.3.1 Nitrogen activation .................................................................................................................... 36

1.3.2 Surface hydrides on RuNPs ....................................................................................................... 37

1.3.3 Arene hydrogenation ................................................................................................................. 37

1.3.4 C=O hydrogenation ................................................................................................................... 38

1.3.5 NO2 hydrogenation .................................................................................................................... 39

1.3.6 Asymmetric hydrogenation ....................................................................................................... 39

1.3.7 Oxidation ................................................................................................................................... 41

1.3.8 Miscellaneous ............................................................................................................................ 42

1.3.8.1 Cellubiose hydrolysis ........................................................................................................ 42

1.3.8.2 Hydrogen Generation ........................................................................................................ 43

1.3.8.3 Synthesis of novel functional materials ............................................................................ 43

1.4 Conclusion ..................................................................................................................................... 44

1.5 References ...................................................................................................................................... 45

Interest in metal nanoparticles (NPs) is increasing dramatically, as reflected by the ever-

1.2.1 RuNPs synthesised directly on supports

Scheme 1. The synthesis of a RuNP-loaded mesopolymer for catalysis. 32

3 –CH2OH (from polyols) + RuCl3 à 3 -CHO + 2 Ru(0) + 6 HCl (1)

In mixtures of methanol/THF of varying composition, this decomposition may take place

Figure 5. HREM image of RuNPs produced inTHF in the presence of PVP.48

Scheme 4. The synthesis of water soluble RuNPs in THF.

1.2.6 Glossary of RuNP syntheses

Ru(COD)(COT) 25 °C, H2 (1 bar) Nitrocellulose/THF 1.0, 1.5, 2.0 47

0 °C, H2 (4 bar) C1C4Im NTf2 1.1 ± 0.2

1.3 Catalytic properties