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Metal–Salen Schiff base complexes in catalysis: practical

aspects
Pier Giorgio Cozzi*
Dipartimento di Chimica ‘‘G. Ciamician’’, Vial Selmi 2, 40126 Bologna, Italy.
E-mail: Piergiorgio.cozzi@unibo.it; Fax: 139 051 209 9456

Received 30th January 2004

First published as an Advance Article on the web 13th August 2004
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Schiff base ligands are considered ‘‘privileged ligands’’1 because they are easily prepared by the condensation
between aldehydes and imines. Stereogenic centres or other elements of chirality (planes, axes) can be
introduced in the synthetic design. Schiff base ligands are able to coordinate many different metals, and to
stabilize them in various oxidation states, enabling the use of Schiff base metal complexes for a large variety of
useful catalytic transformations. Practical guidelines for the preparation and use of different Schiff base metal
complexes in the field of catalytic transformations are discussed in this tutorial review.

1 Introduction active catalytic Schiff base metal complexes are obtained in situ,
and are not well characterized. However, the appropriate
Hugo Schiff described the condensation between an aldehyde choice of metal precursor and the reaction conditions are
and an amine leading to a Schiff base in 1864.2 Schiff base crucial for catalytic properties. Finally, a particular class of
ligands are able to coordinate metals through imine nitrogen Schiff bases will also be discussed. When two equivalents of
and another group, usually linked to the aldehyde. Modern salicylaldehyde are combined with a diamine, a particular
chemists still prepare Schiff bases, and nowadays active and chelating Schiff base is produced. The so-called Salen ligands,
well-designed Schiff base ligands are considered ‘‘privileged with four coordinating sites and two axial sites open to
ligands’’. In fact, Schiff bases are able to stabilize many ancillary ligands, are very much like porphyrins, but more
different metals in various oxidation states, controlling the easily prepared. Although the term Salen was used originally
performance of metals in a large variety of useful catalytic
only to describe the tetradentate Schiff bases derived from
transformations. In this article we show that Schiff bases are
ethylenediamine, the more general term Salen-type is used in
also able to transmit chiral information to produce non-
the literature to describe the class of [O,N,N,O] tetradentate
racemic products through a catalytic process; chiral aldehydes
bis-Schiff base ligands (Fig. 1). Basic guidelines for the design,
or chiral amines can be used. From a practical point of view,
the aspects involved in the preparation of Schiff base metal
complexes are spread out in the literature. We wish to sum-
marize and introduce some practical guidelines for the
preparation and use of Schiff base metal complexes in catalysis.
The present review will focus on the different ways of preparing
metal complexes and their use in catalytic processes. Generally,

Pier Giorgio Cozzi was born in Legnano (Milan) in 1963. He

studied chemistry at the University of Milan, under the guidance
of Professor Cesare Gennari in 1989. After spending four years
as a researcher in Lausanne (Switzerland) with Professor Carlo
Floriani, he was appointed as a Lecturer (in 1994) and then
Associate Professor (in 2000) at the University of Bologna. The
development of new, enantioselective catalytic reactions, the
design of new chiral ligands, and the formation of quaternary
stereocenters using new syn-
thetic methodologies are his
main interests. Professor Pier
Giorgio Cozzi has been a
visiting professor at the Uni-
versities of Aachen (Germany), Fig. 1 Different Salen ligands and M(Salen) complexes.
Neuchatel (Switzerland),
Ottawa (Canada), Basel synthesis and application of metal Schiff base complexes in
DOI: 10.1039/b307853c

(Switzerland), Aarhus catalysis will thus be surveyed with the emphasis on the
(Denmark) and he is a relevant problems in producing active and useful complexes.
member of two European
Networks in the Sixth Preparation of Schiff bases
Framework Program: the
European LigBank and IBA2C Condensation between aldehydes and amines is realized in
projects. different reaction conditions, and in different solvents. The
presence of dehydrating agents normally favours the formation

410 Chem. Soc. Rev., 2004, 33, 410–421 This journal is ß The Royal Society of Chemistry 2004
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of Schiff bases. MgSO4 is commonly employed as a dehydrat-

ing agent.
The water produced in the reaction can also be removed
from the equilibrium using a Dean Stark apparatus, when
conducting the synthesis in toluene or benzene. Finally,
ethanol, at room temperature or in refluxing conditions, is
also a valuable solvent for the preparation of Schiff bases.
Degradation of the Schiff bases can occur during the
purification step. Chromatography of Schiff bases on silica
gel can cause some degree of decomposition of the Schiff bases,
through hydrolysis. In this case, it is better to purify the Schiff
base by crystallization. If the Schiff bases are insoluble in
hexane or cyclohexane, they can be purified by stirring the
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crude reaction mixture in these solvents, sometimes adding a

small portion of a more polar solvent (Et2O, CH2Cl2), in order
to eliminate impurities. In general, Schiff bases are stable solids
and can be stored without precautions. Condensation of
salicylaldehydes or salicylaldehyde derivatives with 1,2-
diamines leads to the formation of one extremely important
class of ligands, generally known as ‘‘Salens’’ (Fig. 1). Salicyl- Scheme 2 Preparation of Schiff base complexes.
aldehydes bearing different substituents are obtained by the
introduction of a formyl group, using a simple and well- commercially available and easy to handle, while the use of
established reaction, into the corresponding phenol derivatives other alkoxide derivatives is more problematic, particularly in
(Scheme 1, a). The combinatorial approach to the discovery of the case of highly moisture-sensitive derivatives of lanthanides.
The reaction of a Schiff base with a metal alkoxide is an
equilibrium reaction and the identity of the species generated is
sometimes difficult to predict. Different complexes can be
present in different concentrations, as a function of the equili-
brium constant. However, the introduction of a bulky group in
the Schiff bases can control the identity and homogeneity of the
complex, by shifting the equilibrium towards the formation of a
single species. The stability of the complexes is regulated by the
equilibrium constant, and a disproportionation between Schiff
base metal complexes and the metal alkoxides can occur. The
disproportionation between the metal Schiff bases and metal
alkoxides is also affected by the substitution pattern of the
Schiff base, but bulky groups normally prevent the Schiff base
complex from undergoing disproportionation. Metal alkoxides
are sensitive to hydrolysis and the presence of adventitious
water can result in the formation of m-oxo species. Addition-
ally, metal Schiff bases bearing alkoxide groups as ligands, are
sensitive to traces of water, producing various m-oxo species.
The presence of adventitious water is difficult to control,
especially when the reaction between the Schiff bases and the
metal alkoxide is performed in situ. The formation of m-oxo
species can cause difficulties in reproducing the results of
Scheme 1 Preparation of Schiff bases. catalytic reactions. Metal amides M(NMe2)4 (M ~ Ti, Zr) are
also highly suitable precursors for the preparation of Schiff
new catalysts is an innovative and exciting area of research.3 base metal complexes of early transition metals. The reaction
Schiff bases are suitable ligands for the preparation of libraries occurs via the elimination of the acidic phenolic proton of the
due to the easy reaction conditions and the variety of chiral Schiff bases, occurring at the same time as the formation of
amines and aldehydes used as precursors. Amino acids and volatile NHMe2. The reaction of Ti(NMe2)4 or Zr(NMe2)4 with
peptides are particularly suitable for the creation of effective Salen gives a Schiff base metal complex bearing two bisamido
catalysts, as indicated in the research of Hoveyda and groups that can be reacted further. The reaction of the bis-
Snapper.4 The condensation of aldehyde-bearing coordinating amido Salen complex with Me3SiCl transforms the bis-amido
groups with amino acids and peptides provides interesting into the bis-chloride complex. A Schiff base metal complex can
Schiff bases, used to make a combinatorial library of ligands.3 be prepared in a clean and effective way using metal alkyl
complexes as precursors (route 3). Various metal alkyls in the
main group of metals (AlMe3, GaMe3, InMe3) are commer-
The complexation steps: different routes cially available and can be used in the preparation of Schiff
In many catalytic applications Schiff base metal complexes are bases by a direct exchange reaction. In this context, particularly
prepared in situ by producing a reaction between the Schiff base suitable for the synthesis of iron, manganese, vanadium and
and available and well-defined metal complexes. This approach copper Schiff bases are the corresponding M(Mesityl)n (M ~
is clearly simple and suitable for catalytic applications. Essen- Fe, Mn, V, Cu, Mesityl ~ 2,4,6-trimethylbenzene) compounds.
tially, five different synthetic routes can be identified for the They are obtained from the reaction of the corresponding
preparation of Schiff base metal complexes (Scheme 2). metal halides with a mesityl Grignard reagent. This reaction
Route 1 involves the use of metal alkoxides (M(OR)n). For only liberates a by-product, 3,5,6-trimethylbenzene (mesityl-
early transition metals (M = Ti, Zr), alkoxide derivatives are ene). Although the synthesis of mesityl metal complex

Chem. Soc. Rev., 2004, 33, 410–421 411

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precursors can be difficult due to their sensitivity, their use the formation of a saturated inactive complex is detrimental to
can avoid the presence of an uncharacterized impurity or the catalysis. The formation of stable or saturated complexes is, of
formation of binuclear complexes. Alkyl titanium and zirco- course, a factor of lack of efficiency in the catalytic process. The
nium tetrabenzyl alkyl complexes are used in the preparation of introduction of bulky substituents near the coordination sites
Schiff base metal complexes, that are active as polymerization can eliminate this problem and enhance the catalytic perfor-
catalysts. These alkyl reagents are obtained from titanium and mance of the Schiff base metal complex, thus preventing the
zirconium halides by the reaction of a benzyl Grignard reagent. early transition Schiff base complexes from forming stable and
As indicated in route 4, many Schiff base metal complexes can catalytically inert octahedral complexes. Metals coordinated to
be obtained through the treatment of the Schiff base with the Schiff bases can transmit chiral information via the coordina-
corresponding metal acetate, normally by heating the Schiff tion of the electrophile to the Lewis acidic center, or via an
base in the presence of the metal salt under reflux conditions. activation of the nucleophile. Metal Salen complexes have the
Copper, cobalt and nickel Schiff bases are prepared using the unusual characteristic of activating, in certain reactions, both
corresponding acetate M(OAc)2 (M ~ Ni, Cu, Co). Instead of the nucleophile and the electrophile. In the transfer of carbene,
using acetate, a direct exchange with metal halides is also
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nitrene or oxene (Fig. 2), the structure of Salen influences the

possible. In fact, early transition Schiff bases are sometimes
prepared by direct reaction with TiCl4 or ZrCl4. All the
methods presented (routes 1–4) are used for Schiff bases or
Salen metal complexes. The synthetic scheme presented in
route 5 is quite effective in obtaining Salen metal complexes. It
consists of a two-step reaction involving the deprotonation of
the Schiff bases and a successive reaction with metal halides.
Deprotonation of the acidic phenolic hydrogen can be realized
using lithium bases (MeLi, BuLi). However, since lithium
alkyls can attack the imine group of the Schiff base, it is
advisable to perform the deprotonation step with NaH or KH
in coordinating solvents. The deprotonation step is normally
rapid at room temperature, but heating the reaction mixture to
reflux does not cause decomposition. Use of excess NaH and
KH is recommended, when the Na and K Salen obtained are
soluble in the reaction solvent. THF is the solvent generally Fig. 2 Different approaches of a substrate to the Salen complex.
used for this type of preparation, and the sodium or potassium
hydride used in excess can be eliminated by filtration, when incoming trajectory of the substrate and its orientation.
the formation of the Na2(Salen) or K2(Salen) is complete. Although stereogenic centres are normally placed in the
The reaction scheme is quite general, and metal halides diamine moiety, subtle conformational effects transfer the
other than titanium and lanthanides could be used. Instead chiral information. M(Salen) can adopt different conforma-
of adding the metal halides to the reaction mixture, the use tions, as shown by crystallographic studies.
of available tetrahydrofuranyl adducts, such as TiCl4(THF)2, While a few M(Salen) complexes show planar conforma-
ZrCl4(THF)2, or VCl3(THF)3, is more effective. When not tions, most of the examples reported in the literature show
commercially available, the tetrahydrofuranyl adducts of metal a bowl (or umbrella, Fig. 3A) conformation, and a stepped
halides are easily prepared by the addition of THF to metal
halides in a different solvent, normally CH2Cl2. Tetrahydro-
furanyl adducts are moderately sensitive salts, and can rapidly
be handled freely in air. However, in the case of the more
sensitive VCl3(THF)3 and TiCl3(THF)3 this procedure is not
recommended. When large amounts of Salens are available, Fig. 3 Different shapes of Salen complexes.
performing the synthesis on a large scale could be recom-
mended using route 5. However, this synthetic strategy can non-planar conformation is also assumed by the complex in the
create problems in the purification steps, during the isolation of solid state (Fig. 3B). In the stepped conformation, the degree of
the Schiff base metal complex. The reaction of Na2(Salen) or folding is correlated to the size of the metal, its oxidation state,
K2(Salen) with metal halides generates sodium or potassium the absence or presence of apical ligands, and the nature of the
salts as by-products. Generally, the formation of the Salen substituent. Cr(V)(Salen) is folded, while the corresponding
metal complex via route 5 is performed in THF and the Cr(III)(Salen) is near planar.5 The conformation of Salen in the
insoluble sodium or potassium halides obtained as by-products
particular oxidation state influences the trajectory of approach
can be eliminated by filtration. However, as the oxygens of the
of the incoming substrate. Therefore, bulky groups on the
M(Salen) are Lewis basic centers, coordination of sodium or
aromatic aldehyde do not block the approach but regulate the
potassium halides could result, leading to many problems in the
orientation of the incoming substrates, determining a high
purification of the Schiff base metal complexes. For catalytic
diastereofacial preference.
purposes, when synthesis is performed in situ by route 5, the
When different elements of chirality are present in the same
presence of coordinated salts can alter the catalytic perfor-
mance of the Schiff base metal complexes. ligand, the conformational effects are more pronounced. This is
the case for the Salen described by Katsuki5 (Fig. 4).
M(Salen) like 8 and 9, with a chiral binaphthyl or similar
Substitution and conformational effects in Schiff bases structure, belong to the second generation of M(Salen).
Coordination of the metal with bi- or tridentate Schiff bases M(Salen), when different chiral elements are not combined,
can produce dimeric, or a saturated metal complex. Particu- belongs to the first generation. The ligand conformation in
larly with early transition metals, which have a tendency to Fig. 4, where a binaphthyl unit is combined with diamine con-
coordinate ligands in an octahedral manner, the complexation taining stereogenic centers, is dictated by at least two factors.
step realized in situ can produce a saturated octahedral com- The combination of stereogenic elements controls the folding.
plex. When chiral Schiff bases are used in the catalytic process, The binaphthyl ligands bring an aryl group close to the metal.

412 Chem. Soc. Rev., 2004, 33, 410–421

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and electronically. Schiff base complexes of early transition

metals are active catalysts for polymerization, provided that
some simple criteria in the synthetic design are met.6
The coordination of phenoxy-imine to zirconium and
titanium displays a distorted octahedral structure, with two
nitrogen atoms and two chlorine atoms in cis position. It is
important to realize that several isomers are possible, and the
stability and reactivity are functions of the substituents of the
Fig. 4 The second generation of Salen. Schiff bases. The introduction of bulky groups in the phenoxy
ring near to the oxygen is important, in order to stabilize these
The polar p-interactions occurring between the aryl group and Schiff bases and make them synthetically useful for poly-
an apical ligand, usually water, can act synergistically with a merization. Interestingly, the octahedral and C2-symmetric
folding effect. The folding effect, deriving from the conforma- Ti- and Zr-bis(phenoxyimine) complexes are chiral at the
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tion imposed by the chelating diamine moiety, is thus enhanced metal, with the titanium assuming a fluxional L or D con-
in these Salens, compared to other Salen metal complexes. figuration (Fig. 7).
On the other hand, these effects can act conversely, reducing
the folding. In general, the fact of the absence of an axial
coordinating ligand can either reduce or enhance the folding of
the metal complex. This is important for the transmission of
chiral information. Theoretical calculations have shown that
axial donor ligands, which change the conformation of the
catalyst, bring the metal closer to the substrate in rate-
determining stereoselective processes, enhancing the enantios-
electivity (Fig. 5).

Fig. 7 A fluxional octahedral Schiff base complex.

Fig. 5 Effect of an axial ligand on the Salen complex.
Although the rapid exchange in the polymerization process is
beneficial to stereocontrol, the formation of different diaster-
eoisomers can cause low stereocontrol in other reactions,
2 Chiral Schiff bases of early transition metals especially if stereogenic centers are inserted in the ligands. For
The Ziegler–Natta catalyst was originally based on the com- this reason, the chiral Schiff bases employed in catalysis with
bination of TiCl4 with alkylaluminium, and it was soon early transition metals have been designed specifically to avoid
discovered that MgCl2-supported titanium was more stable the problem. Two solutions have been indicated by various
and more active. The breakthrough, due to the introduction authors in the course of their studies on the use of Schiff base
of group 4-metallocene as a well-defined metal complex, in early transition metal complexes: a) the use of tridentate or
combination with partially hydrolyzed trimethylaluminium tetradentate Schiff bases; b) the use of Salen as a rigid
(methylalumoxane, MAO), has made the industrial application tetradentate coordinating framework. Tridentate Schiff base
of these catalysts possible. Soon it was realized that a system ligands have been used successfully in several asymmetric
able to mimic the coordination properties of metallocene would catalytic reactions. In this type of catalysis, the size of the
be able to perform polymerization as well. In this context Schiff substituents on the periphery of the ligand plays a key role in
bases were widely used, because they can control the coordina- determining the enantiomeric excess of the product. The
tion properties of the metal and form a coordination environ- reaction with Ti(OiPr)4 and Schiff base ligands is clean only if
ment, similar to a metallocene (Fig. 6). In fact, Schiff bases the R1 group is bulky (Scheme 1). When R1 is not bulky, two
ligands can coordinate titanium, even if it is present in
stoichiometric amounts. Thus, the reaction between a triden-
tate ligand and Ti(OiPr)4 can give three different isomers. A
tbutyl group is normally sufficient to control the formation of
an active monomeric species, while groups such as hydrogen,
bromine or methoxy result in significant amounts of diaster-
eoisomeric titanium species. The octahedral titanium species
containing two ligands are inactive because of this kind of
reaction, and, in general, this can be assumed in other reac-
tions, if a Lewis acidic titanium centre is needed. Most
importantly, the formation of the diastereoisomeric L*2Ti
Fig. 6 Formal equivalence between indenyl complexes and Schiff species reduces the number of catalytically active species and,
bases. when the percentage of L*2Ti is greater, the concentration of
free titanium isopropoxide able to catalyze processes resulting
possess many interesting characteristics. They are moderate in no stereoselection is higher. These considerations have a
electron donors, with a chelating structure and a low electron practical importance in the design of proper, successful Schiff
counting number. In addition, a large library of Schiff bases bases in catalytic processes. Chiral tridentate Schiff bases are
can easily be generated, with structural diversity, both sterically used with vanadium to promote the asymmetric oxidation of

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sulfides, disulfides, and thioacetal. The importance of these

results stems from the simple preparation of the vanadium
Schiff base metal complexes and from the importance of the
enantioenriched products obtained.7 Also, in the case of
Ti(Salen) complexes different species are formed by the
reaction of Ti(OiPr)4 and chiral Salen. Traces of water are
responsible for the formation of oxo species. Oxo titanium
species (Fig. 1, 7, M ~ Ti(O)) are clearly shown to be effective
catalysts by Belokon and North for the enantioselective addi-
tion of Me3SiCN to aldehydes and ketones.8 Also, the corres-
ponding chiral VO(Salen) 10 (Fig. 1, 7, M ~ V(O)) is an
effective catalyst. Metal Salen oxo species are stable to mois-
ture and can be used for catalytic reactions in environmentally-
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friendly catalytic conditions. Detailed mechanistic studies have

shown that the active species in this reaction is a bimetallic
Scheme 3 Coupling of a metal Schiff base promoted by a reductant.
titanium complex.9 The reaction shows one of the peculiar
characteristics of the Salen metal complexes: the ability of a
Salen metal complex to act cooperatively (Fig. 8). This unique to react with oxygen and organic molecules. A key point in the
development of redox chemistry, particularly catalytic redox
chemistry with Schiff bases, is the control of the deactivation of
the system and possible dimerization via coupling of the imino
group. Redox transformations, based on titanium and
vanadium, are well known.10 In fact, titanium in a low oxida-
tion state was reported to perform useful C–C bond-forming
reactions by McMurry.11 Different methods employing various
titanium salts have successfully been introduced. For all of
these, titanium is used in stoichiometric amounts. Recently,
Fürstner introduced a catalytic variant of these methods.12
Catalytic redox reaction is based on two concepts: the use of a
metal able to reduce the titanium complex in the active form,
although not interfering with the C–C bond-forming reaction,
and the use of an oxophilic additive as a mediator of the
catalytic cycle. Chlorosilanes and silicon hydrides appear to be
suitable additives.
Schiff base complexes are able to stabilize titanium in a low
oxidation state and enable the control of simple diastereoselec-
tion in the pinacol coupling of aromatic aldehydes.13 The
reactions are performed using the protocol developed by
Fig. 8 Ti(Salen) catalysed addition of Me3SiCN to aldehydes via
activation of both electrophile and nucleophile. Fürstner. The presence of the oxophilic additive Me3SiCl
does not decompose the Schiff base titanium complexes. Low
valent chiral titanium Schiff bases mediate the enantioselective
behaviour, which is more pronounced in other M(Salen) (Cr, pinacol coupling of aromatic aldehydes (Scheme 4).14 The
Co) mediated processes, is highly advantageous for designing
processes in which activation of nucleophile and electrophile is
necessary.
The advantages of working with VO(Salen) are the high
stability of the complex and simple synthesis from commer-
cially available VOSO4. However, it is necessary to perform the
synthesis under nitrogen or argon, to avoid the formation of
cationic V(V)O(Salen). Various titanium Salen Schiff bases can
also be prepared by direct exchange with TiX4, or by reaction
with a sodium or potassium salt of the Schiff bases.7 These
Ti(Salen)X2 complexes contain two reactive sites, but attempts
to alkylate TiLX2 could result in decomposition, reduction or
the migration of the alkyl group to the imino group of the
Schiff base. The redox chemistry mediated by vanadium or
titanium Schiff bases can involve variations in the oxidation Scheme 4 Enantioselective pinacol coupling promoted by Ti(Salen).
state of the metal or the ligand. In fact, with some Schiff bases,
chosen specifically because they have highly delocalized p unsubstituted Salen gives the highest enantiomeric excess. On
electrons, as in Salophen or [N,N-phenylenebis(salicyleneimi- the other hand, bulky groups need to be introduced with
nate)] (Fig. 1, 2), the reduction of the metal becomes extremely tridentate Schiff bases in order to stabilize the Ti(III) Schiff
difficult. This is an important aspect to evaluate when working base.13 In the enantioselective pinacol coupling reported by
with Schiff bases. Oxidation or reduction can occur exclusively Joshi,14 the author describes an interesting synthetic approach
to the ligand. The consequent reductive coupling of the imino towards Ti(Salen)Cl2 11 (Fig. 1, 6, M ~ TiCl2) avoiding the use
group across two monomeric units of Schiff bases leads to the of TiCl4 or NaH, or KH.
formation of a C–C bond (Scheme 3). The Ti(Salen)Cl2 11 is formed by treating the corresponding
Although the electrons received by the system are stored in a Ti(Salen)(OiPr)2 with Me3SiCl. Hoveyda, Snapper and
C–C bond, reduced vanadium and titanium Salophen are able coworkers have used peptide Schiff base ligand libraries in

414 Chem. Soc. Rev., 2004, 33, 410–421

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the presence of Ti(OiPr)4 to promote the addition of Me3SiCN Br, I), M(Salen)X are prepared using the alkyl reagents R2MX
to epoxides and imines.15 In a mechanistic analysis of the (X ~ Cl, Br, I). Difficulties in the isolation and characteriza-
reaction, the cooperative role of the Schiff base peptide ligand tion of the complexes can arise from the low solubility of the
was disclosed. These Schiff base peptide ligands are modular complexes. It is worth noting that Schiff base complexes can
ligands consisting of three assembled fragments. All three also combine and, sometimes, the oxygen atom of a Schiff base
fragments of the peptide catalyst work together in delivering can become the sixth ligand donor. In order to facilitate the
the nucleophile (CN2) to the substrate, coordinated to the isolation and characterization of Schiff base complexes, the
titanium.16 This is another example of the cooperative introduction of a tbutyl group in an ortho or para position, on
mechanism acting in asymmetric catalysis. Modular ligands the aromatic aldehyde, makes the complex soluble even in
assembled with different parts can be advantageously exploited hydrocarbon solvents. The structural characterization of the
whenever activation of both nucleophile and electrophile is compounds shows five-coordinate complexes that can be
necessary. Zirconium Schiff bases are well known, easily trigonal bipyramidal, or square pyramidal, depending on the
prepared by exchange with Zr(iOPr)4 or by the addition of nature of the backbone to which the two nitrogen atoms are
ZrX4(THF)2 to the sodium or potassium salt of the Schiff
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connected. The greater the flexibility of the backbone, the more

bases. Although chiral zirconium Salens are rarely used in frequently a trigonal bipyramidal geometry is obtained. An
catalysis, an interesting chiral transformation mediated by important aspect of the coordination chemistry of Schiff base
Zr(Salen)Cl2 has been reported. Chiral Zr(Salen)Cl2 12 (Fig. 4, complexes is how the metal is displaced out of the plane of the
9, M ~ ZrCl2) was described as catalyzing a Baeyer–Villinger ligand core. This distance is important in catalysis as it allows
oxidation for particular substrates in a highly enantioselective the transmission of chiral information, and is crucial to the
way.17 On the other hand, zirconium is more electrophilic, and catalytic step. In group 13 Salen complexes this distance is the
the imine of the Schiff bases coordinated to the zirconium is function of the metal radii, and in In(Salen) complexes higher
highly activated. Zirconium Schiff bases can be unstable in displacement normally occurs. Note that the alkyl groups are
the presence of nucleophiles or hydrides. In a recent study, displaced more than the corresponding halides. Alkyl and
Hoveyda reported that zirconium peptide Schiff bases are able chloride Salen complexes are quite robust, and can be handled
to catalyze the addition of zinc reagents to imines.18 However, in the open air without decomposition. This is an important
under reaction conditions, a reduction of the imine of Schiff aspect of Al(Salen) complexes, which can be advantageously
base to the corresponding amine took place.18 Imine bonds used for catalytic applications. The complete displacement of
of the Schiff bases are quite susceptible to reduction or one coordinate ligand from the Schiff base complex causes the
nucleophilic attack, especially when zirconium is coordinated formation of the cationic complex. For example, the dissolu-
to the imino bond. Reduction or alkylation always needs to be tion of the achiral Salen Al(Salen)Cl 13 (Fig. 1, 3, M ~ AlCl) in
taken into account as a possible pathway for the deactivation protic bases (H2O, MeOH), or in the presence of aprotic
of the catalyst, whenever a Schiff base is employed as a ligand. ligands (THF, HMPA), leads to the formation of cationic
hexacoordinate Al(Salen)L2. Interestingly, cationic Al(Salen)
complexes seem to be quite stable, and can also be generated in
3 Chiral Schiff bases of main group metals water. Cationic complexes of Al are involved in the poly-
Group 13 Salen metal complexes are easily obtained from the merization of oxiranes and the polymerization of ethylene.19
reaction of a Schiff base with a group 13 alkyl (Scheme 5).19 Additional reactions were examined, among them Meerwein–
Ponndorf–Meerwein reduction, Friedel–Crafts reactions,
Oppenauer oxidation, phospho aldol reaction, Diels–Alder
reactions and Claisen rearrangements.19 Amido, alkoxy, oxo,
hydroxy, Al(Salen) compounds can easily be prepared by
exchange reactions, using Al(Salen)R alkyl derivatives (R ~
Me, Et). The rapid formation of pentacoordinate compounds
combined with their Lewis acidic properties, make Al(Salen) a
good candidate for catalysis. In this context, Jacobsen reported
the use of chiral Al(Salen)Cl complex 14 in the addition of
HCN to imines (Scheme 6).20

Scheme 5 Preparation of Al(Salen) metal complexes.

Gallium, aluminium and indium Salen metal complexes19 can

be prepared using this protocol. Generally speaking, the reac-
tion is performed in toluene by adding the alkyl derivatives at a
low temperature and warming the solution up to room tem-
perature. Although the complexes are quite stable, care needs
to be taken in the synthesis. In fact, it has been reported that,
with achiral Schiff bases, harsh conditions, such as refluxing in
high boiling solvents, caused alkylation in the imine of the Scheme 6 Catalytic enantioselective addition of hydrogen cyanide to
Schiff bases. In the synthesis of metallic complexes, oxygen- imines catalysed by Al(Salen)Cl.
containing solvents are normally avoided. The Schiff base
metal complex is insoluble, and is recovered by filtration. If the The reaction probably takes place via a double activation
synthesis is performed using a Salen ligand, five-coordinate process, in which one molecule of Al(Salen) delivers the
metal complexes are generally obtained. nucleophile and one activates the substrate. This double
The group 13 metal Salen complexes containing halide (Cl, activation is a general feature in Al(Salen) chemistry and the

Chem. Soc. Rev., 2004, 33, 410–421 415

 View Article Online

Michael catalyzed addition of CN2, CNCH2COOR and N32 underlined the stepwise mechanism of epoxidation, which, to
to amides takes place in this way.21 The formation of the some extent, leads to the formation of a variable amount of
activated catalytic complex is obtained by exchange reaction trans epoxide, when the radical intermediate is stabilized by
in situ and commercially available Al(Salen)Cl 14 is used. The polar substituents on the alkene. The admittance of co-ligands
tendency to exchange the fifth apical coordination site in the to the reaction mixture, particularly pyridine N-oxides, is of
Al(Salen) complex can be attributed to the relatively weak practical importance. The ligand has multiple roles. As
bond between the group 13 element and the group occupying discussed earlier, the ligands force the manganese oxo to
the apical position. This type of bond can be described more come closer to incoming olefins. More importantly, the
appropriately as electrostatic. The particular substrates used in Mn(O)(Salen) is in equilibrium in different forms, while the
the Michael reaction are determined by the propensity of the oxo ligand can coordinate another Mn(Salen). Regarding
Salen to coordinate a carbonyl in the axial position via a epoxidation, the dimer is considered inactive. Axial ligands are
monodentate coordination. a,b-Unsaturated oxazolidinone, or able to stabilize the monomer form of the complex. Easy
other Michael acceptors, are not suitable for this chemistry. catalyst deactivation and irreversible ligand oxidation have
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prompted recent efforts to stabilize the active form of the

4 Manganese and chromium Schiff bases catalyst. This concept is realized by isolating the Mn(Salen)
catalyst through the use of cross-linked polymer supports, and
In 1985 Kochi described the first application of the achiral immobilization in polysiloxane, zeolites or supramolecular
chromium Salen complex in catalysis.22 Careful synthetic and
multimetallic architectures.25
mechanistic investigations have prompted further exciting
Chromium Schiff bases have found some interesting applica-
developments in this field.23
tions in catalysis. Tridentate and tetradentate achiral Schiff
Chiral manganese Salen complexes were described by
bases provide stabilizing ligands for polymerization catalysis
Jacobsen and Katsuki. The chiral ligand 5 developed by
and, due to their accessibility, libraries of ligands are easily
Jacobsen is easily prepared by using accessible methods and
prepared. The introduction of bulky groups in an ortho posi-
reactions.24 The manganese complex 15 (Fig. 1, 7, M ~ MnCl)
is normally prepared using Mn(OAc)2 and subsequent oxida- tion to the phenoxy group is the key action in preparing highly
tion of the intermediate Mn(II)(Salen) by exposure to air. active complexes for polymerization, using late transition
Complexes containing chloride ions are obtained by an metals. The methodology employed for the synthesis of the
exchange reaction performed during work-up, through treat- complex chromium Schiff bases is interesting. The soluble
ment with chloride-containing aqueous solution. On the other organometallic precursor (p-tolyl)CrCl2(THF)3, obtained from
hand, chiral and achiral Mn(II)(Salen) are more difficult to the addition of Grignard reagents to CrCl3(THF)3, is added to
obtain, and much more sensitive. Chiral Mn(III)(Salen) com- the Schiff base. Metalation, with the formation of the
plexes are quite efficient catalysts for the asymmetric epoxida- chromium Schiff bases, occurs by the elimination of toluene.26
tion of cis olefins. Oxidation takes place with PhILO, or The use of organometallic precursors avoids the route via
derivatives, but other oxidants, such as NaClO, H2O2, NaIO4, potassium or sodium salts of the Schiff base and eliminates the
and peracid have also been used (Scheme 7). tedious problem of the purification of NaCl or KCl bypro-
ducts. Chiral tridentate Schiff bases are prepared by a different
route. Jacobsen reported the Cr Schiff base metal complex 17
as a catalyst for highly diastereoselective and enantioselective
hetero Diels–Alder, inverse electron demand hetero Diels–
Alder (Scheme 8), and hetero-ene reactions.27 Catalysis is

Scheme 7 Enantioselective epoxidation promoted by Mn(Salen)Cl.

The key intermediate is an Mn(O)(Salen), studied using

spectroscopic and theoretical calculations. An analysis of the
mechanism of the reactions suggests that a stepped conforma- Scheme 8 Enantioselective hetero Diels–Alder reaction promoted by
tion of the Salen is crucial in transmitting chiral information. a chiral tridentate chromium Schiff base.
The ligand introduced by Jacobsen is now commercially avail-
able, or can easily be prepared, while the ligand described by sometimes performed in the presence of a dehydrating agent as
Katsuki is obtained from Binol (Binol ~ 1,1’-bi-2-naphthol) the structure of the catalyst is dimeric, and the octahedral
following several synthetic steps. Katsuki’s Mn(Salen) complex chromium coordinates water.
16 (Fig. 4, 8, M ~ MnCl, Ar ~ Ph) gave higher turnover The new methodology for the preparation of the catalyst
numbers with respect to Jacobsen’s ligand, but its application is shown in Scheme 8. The coordination of the chromium
in catalytic enantioselective reactions has only been reported on complex takes place by means of CrCl3(THF)3 in the presence
a small scale. It is quite important to note that, in the applica- of a base, such as lutidine. The method for the preparation of
tion of Jacobsen–Katsuki asymmetric epoxidation, olefins achiral and chiral Cr(Salen)X metal complexes is interesting.
bearing aromatic substituents, or bearing double or triple Chiral Cr(Salen)Cl 18 (Fig. 1, 7, M ~ CrCl) is normally
bonds, are normally used. This could be determined by the obtained by using Cr(II)Cl2, which is commercially available,
possible orientation of the alkene when it is approaching and operating under a strictly nitrogen atmosphere. When
the Mn(oxo) derivatives. Theoretical calculations have also complexation of the Salen has occurred, producing a brown

416 Chem. Soc. Rev., 2004, 33, 410–421

 View Article Online

solution, the flask is exposed to the air and stirred. Complexa- by the Cr(Salen) mediated addition of stereogenic allyl halides
tion between CrCl3 and Salen does not take place, and the use to aldehydes, is of considerable interest.31
of Na2(Salen) or K2(Salen) in combination with CrCl3(THF)3
is essential. Synthesis with CrCl2 is sometimes difficult, since
this salt is highly sensitive to the air. Moreover, this route is not 5 Iron and ruthenium Schiff base complexes. A
recommended for certain applications, because CrCl2 contains useful source of carbene
a variable amount of water, which can modify the coordination
A variety of enzymes are able to catalyze different reactions
and properties of the Cr(Salen) obtained. However, water
such as oxidation, reduction and isomerization, containing iron
coordinated to Cr(Salen) is essential to promote a catalytic
bound to porphyrin (Heme). Given the similarity between
cycle. In the addition of Me3SiN3 to epoxides described by
Salen and porphyrins, recent work has been directed towards
Jacobsen,28 the formation of active Cr(N3)(Salen) complex 19
exploiting iron Schiff bases in order to promote different
(Fig. 1, 7, M ~ Cr(N3)) is determined by the water present
catalytic reactions. Preparation of Fe(Salen)Cl 23 (Fig. 1, 3,
in the reaction mixture. The difficulties in obtaining chiral
M ~ FeCl) seems quite straightforward, since FeCl3 hydrated
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Cr(III)(Salen)Cl for epoxidation reaction have prompted

in refluxing ethanol is used, but the material can be con-
Gihleany to explore a different route. The reduction of purified taminated by iron m-oxo species. Dimeric chiral and achiral
Cr(III) performed with Na(Hg) has proven to be an efficient Fe(Salen) m-oxo species are prepared by Nguyen and used in
strategy to prepare the Cr(II) in situ, while allowing the catalytic transformations.32 An interesting approach to the
preparation of chiral Cr(Salen)X complexes.29 Kochi’s work on synthesis of quite sensitive Fe(II)(Salen) considers the use
the epoxidation reaction with achiral Cr(Salen)22 20 (Fig. 1, 3, of an organometallic reagent. Fe2Mes4 is prepared from
M ~ CrCl) did not follow in an efficient enantioselective FeCl2(THF)1.5 using standard mesityl Grignard.33 Fe2Mes4 is
methodology until Gilheany discovered that the epoxidation of a rather sensitive compound, but can react with the acidic
trans olefins can be carried out in the presence of stoichiometric phenolic oxygens of the Salen to produce the formation of
and catalytic amounts of stable oxo Cr(Salen) 21, (Fig. 1, 7, the desired Fe(II)(Salen) in pure forms. Fe(II)(Salen) is sensitive
M ~ Cr(O)) with iodosylbenzene as an oxygen source.30 An to oxygen and moisture, and difficult to handle. The easy
interesting mechanistic analysis of the reaction by DFT oxidation of Fe(Salen) has hampered its use in catalysis.
calculation has shown the intriguing way in which Salen is Different approaches to the synthesis of Schiff base complexes
able to transmit stereochemical information during the using stable precursors have also been considered. Bolm
epoxidation reaction.29 We have presented a different route reported the preparation of a tridentate Schiff base iron
for a chiral Cr(Salen) 22 (Fig. 1, 7, M ~ Cr) for a specific catalyst, prepared in situ from Fe(acac)3, which is able to pro-
application, by reducing the insoluble CrCl3 in THF or in mote the enantioselective oxidation of sufide to sulfoxides.34
CH3CN with solid Mn.31 Other research groups have adopted Although the enantiomeric excesses obtained were inferior to
this methodology for the preparation of optically active the excesses using the same process catalyzed by vanadium, the
chromium complexes. Cr(Salen)Cl 18 has remarkable proper- possibility of preparing libraries of Schiff bases will certainly
ties, and should be regarded as a privileged complex, as it can increase enantiomeric excess. The dimeric m-oxo Fe(Salen)s
be used for many different applications. Jacobsen has described prepared by Nguyen have found an interesting use as stable
catalytic reactions and has discovered an interesting feature of precursors for the generation of iron carbene complexes, able
M(Salen) metal complexes: namely, that there is a cooperative to catalyze the enantioselective cyclopropanation of olefins
mechanism enabling Cr(Salen) to activate the nucleophile and with ethyl diazoacetate.35
the electrophile and assemble them in a well organized transi- The synthesis of Ru(Salen) was realized using a nitrosyl as
tion state. Cr(Salen)Cl 18 is treated with a silver salt (AgOTf, precursor.5 Many ruthenium complexes can serve as catalysts
AgPF6, AgBF4) to promote the formation of cationic chro- for various oxidation reactions. Asymmetric epoxidation can
mium complexes. Chiral cationic Cr(III)(Salen) is able to be exploited by ruthenium complexes to reach moderate levels
promote catalytic enantioselective reactions in which the Cr of enantioselectivity. Nitrosyl chloro(Salen) ruthenium com-
complex behaves like a chiral Lewis acid, as also reported by plexes 24 and 25 (Fig. 4, 8 and 9, M ~ Ru(NO)Cl) are
Katsuki.5 Catalytic redox reaction can also be performed described by Katsuki5 in interesting reactions mediated by
by Cr(Salen)s. The enantioselective version of the Nozaki– visible light. The complex is, in fact, coordinatively saturated so
Hiyama reaction (Scheme 9) was described using a catalytic that irradiation by visible light makes it active, leading to the
dissociation of the apical nitrosyl ligand. An electron transfer
mechanism seems to be involved in these transformations. The
scope of ruthenium Salen epoxidation is quite interesting, since
cis and trans olefins can be epoxidated. Chiral Ru(Salen) 24 is
also used to promote cyclopropanation of olefins. The inter-
mediate carbene is approached by the olefin, and the highly-
stepped second generation of Katsuki’s Salen complexes have
an ideal structure for exhibiting high diastereo- and enantio-
selectivity. The synthesis of Ru(Salen) without the nitrosyl
group was difficult to realize, until Nguyen reported that
ruthenium(II) Salen complexes were a very efficient catalyst for
the cyclopropanation of olefins.35 The key discovery of the
synthesis was the stabilization of the intermediate Ru(II)Salen
by pyridine, as shown in 26 (Scheme 10).
Scheme 9 Catalytic enantioselective and diastereoselective redox
reactions promoted by Cr(Salen).
6 Co(Salen). Useful catalyst for opening epoxides
amount of Cr(Salen) 22.31 The mechanistic analysis of the Achiral Co(Salen) 27 (Fig. 1, 3, M ~ Co) has a well-established
reaction shows that the aggregation between different mole- ability to bind oxygen.36 The square pyramidal coordination
cules of Cr(Salen) is responsible for the enantioselectivity geometry, imposed by the Salen framework, is necessary for
obtained. The simple general syn diastereoselection obtained Co(II) complexes to obtain the correct electronic configuration

Chem. Soc. Rev., 2004, 33, 410–421 417

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molecules. Interestingly, Schiff bases are described and then

used to promote carbene addition, as well as other transforma-
tions. Chiral Co(III)(Salen) 29 (Fig. 1, 7, M ~ Co) has been
used for the kinetic resolution of epoxides promoted by
water.45 The mechanism of the reaction involves double activa-
tion, which is a feature of the Salen complexes. Water coordi-
nated to Co(Salen) is delivered to an epoxide coordinated to
another molecule of Co(Salen). The special spatial arrange-
ment in which the transmission of the chiral information is
maximized was defined by Jacobsen as ‘‘head to tail’’ (Fig. 9).
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Scheme 10 Catalytic enantioselective and diastereoselective cyclopro-

panation catalyzed by Ru(Salen).

for O2 binding. This property has stimulated research into

selective binding of O2 with reversible carriers,37 able to per-
form the catalytic oxidation of organic substrates.38 In
particular Co(Salen) 27 has been used for the preparative
oxydation of phenols, indoles, flavonols and amines. The
electrochemistry and ligand exchange were investigated in
different solvents. The complexation with a stronger donor
molecule makes Co(Salen) a stronger reducing agent. The
binding ability of O2 to Co(Salen)-type complexes depends on
the basicity of the axial ligand. More importantly, oxidation Fig. 9 Supramolecular arrangements ‘‘head to tail’’ between two
takes place via the coordination of the substrate to the cobalt. Salen units.
Organic substrates containing donor atoms (phenols, indoles,
and amines) are more easily oxidized.39 As in Nature, Schiff This particular arrangement is found in many dimeric
base metal complexes were designed to include a cavity, in structures of Salens, and can derive from minimizing steric
order to accommodate dioxygen or some small ligands.40 hindrance between the two Salen molecules. The feature has
However, as already presented in this review, non-covalent been proven by careful kinetic analysis and by the synthesis of
secondary interactions are essential in order to obtain selective different models. This feature is also important in improving
and efficient catalysts with Salen metal complexes. The tailored the catalytic performance of the system, based on Salen. In fact,
design of a Salen cobalt complex with the introduction of non- several oligomeric and dendridic Co(Salen) prepared on the
covalent secondary interactions was recently reported by basis of trial and error, have been used for the kinetic resolu-
Crego-Calama and Reinhoudt.41 Coordination of the donor tion of epoxides,45 showing an increased activity. The new
atom to the cobalt metal center was used in order to insert the frontier in these studies is to build up an innovative geometry
Co(Salen) into an insoluble matrix. Polyaniline appears to be a for a dimeric transition state, in which two molecules of Salen
suitable supporting reagent for Co(Salen), since the presence of are involved, using different reactions and different metals.
nitrogen atoms enables the stabilization of the complexes by
axial coordination.42 Copolymerization of particular Co(Salen)
complexes into porous material provides a reversible oxygen 7 Nickel and copper transition metal Schiff bases
carrier, suitable for the storage/release of gases.43 Schiff bases have an important role to perform as polymeriza-
MetalloSalen cobalt complexes are useful for the transfer of tion catalysts, and are able to stabilize a reactive cationic nickel
carbene and for opening epoxides. The cobalt(II) Salen com- complex. In order to stabilize cationic intermediate nickel
plexes are readily prepared by using Co(OAc)2. The oxidation complexes, the Schiff bases are prepared using the reaction of
from Co(II) to Co(III) can be realized by treating Co(II) with air hindered aromatic amines (2,6-diisopropylaniline) with dike-
and acetic acid, or using various acids in the presence of air. tones. Although Ni(Salen) complexes have not found many
Other counter ions can be introduced by oxidation performed applications in catalysis, their planar coordination geometry
with the cationic ferrocenium Cp2FeX, where X is PF6, BF4. constitutes an interesting platform to coordinate other metals.
Oxidation conducted with ferrocenium gives the soluble Cp2Fe The Schiff bases are able to act as a metalla crown, and an
that can be purified by extraction. Reduction of the Co(Salen) interesting structure containing different metals can result.
27 complex to a formal Co(I) and re-oxidation to Co(III) via Ni(Salen) 30 bearing another metal can behave as a bifunc-
oxidative addition, could be another route for the catalytically tional catalyst, as prepared by Kozlowski (Scheme 11).46
active Co(III)Salen. Co(I)(Salen) 28, an extremely air-sensitive Copper Schiff bases have found a more extensive use, since
compound, is able to activate small and inert molecules, such as copper(I) can be stabilized by Schiff bases and used in nitrene
CO2.44 Reduced Co(I)(Salen) is prepared by treatment of the transfer.47 Schiff bases derived from two types of diamine
Co(II) complex with Na or K sand. An important feature of have also been described.47 The preparation of the complexes
M(Salen) complexes is shown by these cobalt(I) complexes. The generally uses copper(I), but copper(II) sources have also been
Salen is a bifunctional molecule with a Lewis acid (metal considered. Similar results obtained in nitrene transfer are
center) and Lewis basic center (oxygen of the Schiff bases). probably due to the fact that a reduction of copper(II) to
Coordination of the Na or K molecules takes place through the copper(I) takes place, determined by the nitrene source. Due to
oxygen of the Salen. Activation of the inert CO2 takes place the particular geometry and properties of the Schiff base,
through the two metals.44 Addition of carbene by Co(Salen) Cu(Salen) 31 (Fig. 1, 6, M ~ Cu) is able to coordinate ions, via
is described by different groups with different Salen-type the interaction with the oxygen of the Schiff base.48 The

418 Chem. Soc. Rev., 2004, 33, 410–421

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addition of other organometallic reagents as well. Alkynylation

has attracted considerable interest in recent years, as pro-
pargylic alcohols are valuable synthetic precursors. The
undeveloped addition of alkynyl zinc reagents to ketones
can be realized using Zn(Salen) as a catalyst, leading to new
perspectives in the formation of quaternary stereocenters
(Scheme 12).52
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Scheme 11 Michael catalyzed addition by a bimetallic Ni(Salen)

complex.

complexes are prepared by the reaction of Salen with copper

acetate in ethanol. The Cu(Salen) is stable when exposed to air
and moisture, and it is possible to perform enantioselective
alkylation in phase transfer conditions. Scheme 12 Catalytic enantioselective alkynylation of ketones pro-
moted by Zn(Salen).

8 Zn(Salen): catalytic addition of organometallic

reagents 9 Lanthanide metal Schiff bases
Several reports describe the synthesis of zinc(II) Salen com- Ligands able to coordinate lanthanides exhibiting a low
plexes from either Zn(OAc)2 or ZnCl2/Et3N. However, these coordination number can be considered a primary topic in
routes can create some difficulties in isolating a pure metalated modern f-element chemistry. Schiff bases, because of their
product. In some cases a mixture between the complex and the simple synthesis, are a valuable alternative to the widely-
free Salen is isolated. A more direct route is the treatment of employed and studied cyclopentadienyl framework. One of the
Schiff bases with the reactive alkyl derivatives ZnMe2 or ZnEt2. great problems in coordinating lanthanide with Schiff bases
This strategy is an advantage compared to the use of Zn salts, derives from the small charge to the radius of the ions. In fact,
since both alkyls are commercially available in toluene solution lanthanides prefer to use higher coordination numbers.
or hexane solution. Isolation of Zn(Salen), and its character- Lanthanides coordinated to Schiff bases have the propensity
ization by X-ray analysis, are facilitated by the use of pyridine. to yield dinuclear or polymeric species. Dianionic tetradentate
On the other hand, without pyridine the complex can be ketoiminato Schiff base complexes can be prepared with low
isolated in polymeric form, where the oxygen of the Schiff coordination number by the introduction of a bulky imido or
base coordinates the zinc of another molecule of Salen. aryloxo group. The starting material for the preparation of
Another possible Zn derivative for the synthesis of Zn Schiff lanthanide Schiff base complexes is crucial, as well as the
bases is Zn[N(SiMe3)2]2. The use of this reagent is particularly consideration of the ionic radii of the lanthanides employed.
recommended for bidentate Schiff bases, because it is possible Higher coordination numbers are obtained by producing a
to avoid the formation of fully coordinated Zn Schiff base reaction between the larger La or Nd and the Schiff bases. The
complexes. The intermediate Zn(Schiff base)hexamethylsil- choice between coordinating and uncoordinating solvents is
amide can be used as a starting material for the preparation also important. To isolate a mononuclear lanthanide complex
of three mixed coordinated unsaturated (salicylaldiminato)- from a reaction of a Schiff base with a larger lanthanide, it is
Zn(OR) complexes (where R ~ Me, Ph, or OCOMe), which necessary to perform the synthesis in coordinating solvents, i.e.
are useful for catalytic applications. As in the case of Al(Salen), THF. The coordinating solvent can bind to the metal ion, and
chiral Zn(Salen) 32 (Fig. 1, 7, M ~ Zn) shows interesting is capable of preventing the formation of dimers or polymers.
photophysical properties, and the luminescence of the complex The synthesis of lanthanide Schiff bases is realized by the
is well recognized during its preparation.49 Due to their employment of suitable precursors. Anhydrous lanthanide
stability in aqueous systems Schiff bases can be suitable for trichloride is accessible by different synthetic methods. If the
carrying active metals and investigating photophysical pro- lanthanide Schiff base is prepared by route 5, purification of the
perties in biological systems. One of the reasons why it is complex is quite difficult as the Schiff base tends to bind
difficult to crystallize anhydrous Zn(II) Salen complexes can be sodium or potassium chloride. An alternative preparation uses
ascribed to the ability of Salen oxygen to coordinate metal alkyl lanthanides. These are usually quite difficult to obtain,
and salts, even after chelation. This property can be used and only a few reports concerning the synthesis of these species
advantageously to develop new catalytic reactions. Zn(Salen) have been published to date. Another possible synthetic route
32 can catalyze the addition of ZnEt2 to aldehydes. We have for lanthanide Schiff bases involves special silylamide
reported the use of Salen in this ‘‘privileged’’ reaction,50 and Ln[N(SiHMe2)2]3. The use of other silylamides is problematic,
Kozlowski51 has modified the structure of Salen, using the and can lead to insoluble oligomeric complexes. The use of a
same concepts and enhancing the reactivity of the system. Salen special silylamide enables the coordination of the silicon atom
can act as a bifunctional catalyst, mimicking the common to the lanthanide center. The imido complexes of lanthanide,
aminoalcohols widely used in Zn-mediated additions of Et2Zn resulting from this synthetic route, are interesting reactive
to aldehydes. Zn(Salen) 32 has the ability to promote the intermediates for catalytic chemistry. In fact, an interesting

Chem. Soc. Rev., 2004, 33, 410–421 419

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application of lanthanide Schiff base complexes in catalysis has substrate activation. Molecular recognition, supramolecular
been recently reported. RajanBabu53 described an interesting interaction and host–guest chemistry will almost certainly be
yttrium complex surrounded by chiral Salen 5 in the catalytic used to design the next generation of chiral Schiff bases.
kinetic resolution of alcohols. The complex is prepared by the
silylamide route. X-ray analysis shows that the large yttrium
ion is placed above the N2O2 plane, and two cis oriented Acknowledgements
coordination sites are probably involved in the catalytic
reaction. Morken describes another active yttrium complex, I would like to thank Sandro Gambarotta for sharing the finer
prepared by a different route in the enantioselective variant of a points of science, discussion and unpublished reports about
Tishchenko reaction.54 The combination between yttrium and Schiff base complexes. I would like to thank all my past and
the chiral Salen 5 was found in a combinatorial approach, in present coworkers for their enthusiasm and skill, and for their
which several other ligands and metals were examined. The practical efforts and contribution to the catalytic applications
complex prepared using Y5O(OiPr)13 is seven-coordinated and of Schiff base metal complexes. Dr Eleonora Rivalta is
acknowledged for proof reading. I am grateful for the financial
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bridged by two hydroxide ions to a second yttrium atom. The

structure is considerably folded. Lanthanides in a low oxida- support of this work by MIUR (Stereoselezioni in chimica
tion state are important, and are used in organic chemistry. organica, metodologie ed applicazioni), FIRB (Progettazione,
Low valent samarium iodide (SmI2) introduced by Kagan, has preparazione e valutazione biologica e farmacologica di nuove
found extensive use in redox chemistry, in the formation of molecole organiche quali potenziali farmaci innovative) and
organosamarium(III).55 Chiral samarium complexes are still the University of Bologna (Funds for selected research topic).
rarely developed, and Schiff bases provide an advantageous use
of ligands, available on a large scale for stoichiometric
enantioselective reactions. Unfortunately, Schiff bases are References
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Scheme 13 Stabilizing Sm(II) with pyrrole Schiff bases.
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