CHM 203: Inorganic Molecules,

Materials & Medicines

Lecture Part II (4-6)

Basker Sundararaju
basker@iitk.ac.in
 Disclaimer

The material used throughout this course are taken

from various books/web sources. It is only meant for
teaching purpose and does not have any commercial
aspect in it.
Overarching the Goals of Catalysis Research
A typical Catalytic Cycle
 Milestones in Organometallic Chemistry
Paul Ehrlich V Grignard and P Sabatier K. Ziegler and G. Natta G. Wilkinson and E. Fischer H.C.Brown and G. Wittig
(1908) (1912) (1963) (1973) (1973)

OrganoArsenic
Grignard Reagent Ziegler Natta Polymerization Sandwich Compounds Hydroboration/Olefination
compound

R. Hoffman and K. Fukui Knowles, Noyori and Chavin, Grubbs and Suzuki, Negishi and
(1981) Sharpless (2001) Shrock (2005) Heck (2010)

Reaction Mechanism Asymmetric Catalysis Olefin Metathesis Cross-coupling

 Why Study Organometallic Chemistry?
• Fundamental Science: Understanding the nature of the interesting and useful
complexes.
• Organic Synthesis: Organometallic Complexes allow many powerful synthetic
organic transformations that can not be accomplished without metals,
including Heck, Suzuki, asymmetric hydrogenation reactions.
• Bulk Chemical Synthesis and Catalysis: Huge industrial importance to
organometallic processes, including commodity chemicals, plastics,
petroleum, etc.
• Material Science: Chemical vapor deposition for depositing thin-films of
metals. Complex organometallics for advanced materials, such as organic light
emitting diodes.
• Bioinorganic Chemistry: Some overlap, such as with Vit. B12, hydrogenase,
carbonylase, etc.
• Energy Science: Emerging subfield of catalysis.
 Importance of Organometallic Transformations
Acetic Acid 1700 metric tons (1990)

Co(II)
CH3 2 CH3CO2H + H 2O
+ 5/2 O2
H 3C

Waker Process: 273 metric tons (1990)

PdCl 4²- / Cu+

C2H 4 + 1/2 O2 CH3CHO

Terephthalic acid and ester synthesis: 3496 metric tons (1990)

CH3 CO2H
Co(II), Mn(II)

OAc-, Br -
CH3 CO2H
 Importance of Organometallic Transformations

Hydroformylation: 1820 metric tons (1990)

Co2(CO)8 CHO
+ CO + H2 CHO
R R +
R Me

Polymerization: 12,000 metric tons (1990) now 1011 lbs of polymer a year

Ni complexes
R Polymer(s)
Z-N catalysts, others
 History: Cadet’s Arsenical Compound

• French Pharmacist-chemist, Louis Claude Cadet de Gassicort (Paris): (1760)

• Burns on exposure to air
• Predates the discovery of O2 (1778) and carbonated water (1767)

Me Me
As2O3 + CH3CO2K As As
Me Me

See editorial: Seyferth, D. Organometallics 2001, 20, 1488 -1498

 Zeiss Salt (1825)
H -
H
EtOH KCl Cl
Pt(IV)Cl 4 + Pt(II)Cl 2 Black Solid Cl Pt
heat H 2O Cl H
H

• Danish pharmacist Zeiss.

• First organometallic isolated in pure form.

• Correct formula by Zeiss, confirmed in 1861.

• Correct structure proposed by Dewar in 1951.

• X-ray in 1954

Zeise, W. C. Ann. Phys. 1831, 97, 497–541.

Seyferth, D. Organometallics 2001, 20, 2-6.
Koetzle,T. F. Inorg. Chem. 1975, 14, 2653–2657.
 Later in the 19th Century
• Diethyl Zinc (1848), Edward Frankland

2 Zn + Et I ZnI2 + Zn(C2H 5)2

Frankland, E. Q. J. Chem. Soc. 1850, 2, 263-296.

See: Seyfertth, D. Organometallics 2001, 20, 2940-2955.

• Organochlorosilanes (1863), Charles Fridel and James Crafts

• Ni(CO)4 (1890), Ludwig Mond

CO
50 °C
Ni + 4 CO Ni
CO
OC
CO

Mond, L. J. Chem. Soc., Trans. 1890, 57, 749-753

 Later in the 19th Century

• 1893, Alfred Werner develops modern theory of coordination chemistry

• Heterogeneous alkene hydrogenation (1897). Paul Sabatier (Noble Prize in

1912)

• Grignard Reagents (1899), Francois Auguste Victor Grignard (Noble Prize in

1912)

Mg + R-X R-Mg-X
 Early 20th Century
• Hein (1919) Chromium 𝜋-complexes

CrCl3 + PhMgBr [Cr(Ph)n ]0,+¹ n = 2,3,4 Cr

• Fischer-Tropsch Synthesis (1925)

Heterogeneous
Catalyst
Coal CO + H 2 Hydrocarbons

Fuel Synthesis for WWII Germany and South Africa.

 Other Notable OM Complexes

Me H
OC CO
Me Pt I Fe
OC CO
Me H

First TM-alkyl Complex First TM-Hydride Complex

Pope, 1909 Hieber, 1931

Fe
CO
OC CO

First TM-Diene Complex

Reihen, 1930
Ferrocene – Modern Organometallic Chemistry’s Era begin

FeCl 3
H Fe(0) + N 2
MgBr
NR 3

C10H 10Fe
Cp2Fe, "Ferrocene"
Keary, T. J.; Pauson, P. L. Miller, S. A.; Tebboth, J. A.;
H
Nature, 1951, 168 , 1039-1040. Tremaine, J. F. J. Chem. Soc.
Fe 1952, 632-635.
H

However:
• MP = 174 ∘C without decomp!
• Stable in air to 500 ∘C
• Stable in Conc. Boiling HCl
Ferrocene – Modern Organometallic Chemistry’s Era begin
• Wilkinson and Woodward (1952)

Fe

Wilkinson, G.; Rosenblum, M.; Whiting, M. C.; Woodward, R. B.

"Sandwich complex" JACS 1952, 74, 2125–2126.
See: Wilkinson,G. JOMC 1975,100, 273–278.

• Note: Wilkinson and E. O. Fisher, 1973 Nobel Prize for work on sandwich complexes.

• Historical importance: First example of a robust organometallic complex, and demonstrated

that ligands design can effect stability.
 ‘Modern’ Landmarks
• 1955, Ziegler and Natta develop olefin polymerization using hetereogenous
mixed metal system.
• Nobel Prize 1963.

TiCl4 + AlEt3 + CH2=CH2

n

high mw polyethylene

• 1962, Vaska’s Complex, Reversible Binding and OA/RE

H2 H
O O2 Ph 3P H
Ph 3P Cl
Ph 3P O Ir Ir
Ir PPh 3
OC PPh 3 OC
OC PPh 3 Cl
Cl
Vaska's Complex
 ‘Modern’ Landmarks
• 1964 – Fischer reports first metal carbene.
CO Br
OC CO
OC CO
W W
OC CO
OC CO
Me OMe
Me

Stabilized, Fischer Carbene Carbyne Complex

1964 1973

• 1974 – Schrock synthesize metal alkylidene complex

• Helps establish olefin metathesis – lead to 2005 Noble for Schrock, Grubbs and Chauvin.
tBu
Me Cl
Cp tBu
Ta Ta tBu
Ta
tBu
CH 2 Ph 2P
Cp
tBu tBu PPh 2

First Alkylidine First Methylene Complex First Alkylidyne

1974 1975 1976
 ‘Modern’ Landmarks
• 1961, Heck and Breslow propose Correct Mechanism for hydroformylation.

HCo(CO) 4 H O Heck, R.; Breslow, D.

R J. Am. Chem. Soc.
R H
1961, 83, 4023-4027.
CO, H 2

• 1965, Wilkinson (and independently Bennet and Coffey) report (PPh3)3RhCl as a

homogenous catalyst for alkene hydrogenation, becomes known as Wilkinson’s Catalyst.

Ph 3P Cl Osborn, J. A.; Jardine, F.

H.; Young, J. F.; Wilkinson,
Rh G. J. Chem. Soc. A. 1966,
PPh 3 1711-1732.
Ph 3P
 ‘Modern’ Landmarks
• 1968, Knowles Reports First Example of Catalytic Asymmetric Hydrogenation
• Leads to Nobel Prize in 2001 to Knowles, Noyori and Sharpless.

CO2H CO2H
RhCl 3(P*PhMeiPr) 3 - 0.15 mol%
Knowles, W. S.; Sabacky, M. J.
Me Chem. Commun. (London)
H2 1968, 1445-1446.

15% ee

• 1972 Mizoroki and Heck Independently Report First Catalytic Heck Reaction
• Leads to Nobel Prize for Heck, Suzuki and Negishi in 2010.

Pd(OAc) 2 (1 mol %)
I Heck, R.; Nolley, J.
Bu 3N
+ J. Org. Chem.
1972, 37, 2320.
 ‘Modern’ Landmarks
• 1982, Bergman Reports first example of bimolecular oxidative addition to
C-H bond of an alkane.

Me Me Me Me
H
Me Me

Me Me H
+ H Ir
Me Ir Me
Me 3P H Me 3P

Janowicz, A. H.; Bergmann, R. G.

J. Am. Chem. Soc. 1982, 104 , 352-
354.
 Power of Catalysis

Nobel Prize in Chemistry (TM Catalysis)

2001 2005 2010

Asymmetric Catalysis Olefin Metathesis Cross-coupling

Source image: Google

 Key players in olefin metathesis
Olefin Metathesis
2005
Nobel
prize
winners

Key players in olefin metathesis

Deryn Fogg Karol Grela S. Kotha (India)

 Olefin Metathesis – Timeline
Metathesis, which literally means to change places, provides a way of breaking and remaking carbon-carbon
double bonds.

- 1957 by Herbert Eleuterio at DuPont reported the discovery of unsaturated polymers from olefins
- 1957, Propene could be converted into butene and ethene when treated with a mixture of triisobutyl
aluminium and molybdenum oxide on aluminium oxide.
- Much later from Industry, Nissim Calderon at the Goodyear Tire and Rubber Company, US. Caulderon showed that the
same type of reaction, which he termed olefin metathesis, took place in both processes.

- However, the mechanism underlying metathesis remained a mystery.

R.H. Grubbs, Nobel Lecture, 2005.
N. Calderon, E. A. Olfsead, J. P. Ward, W. A. Judy, K. W. Scott, J. Am. Chem. Soc., 1968,,90, 4133
J. L. Herisson, Y. Chauvin Makromol. Chemie, 1971, 141, 162
 Olefin Metathesis – Timeline
1967-1975 Puzzle period for finding out the mechanism for this crazy reaction?

Caulderon Pair-wise conventional Mechanism

Chauvin’s Metallacyclobutane

R.H. Grubbs, Nobel Lecture, 2005.

N. Calderon, E. A. Olfsead, J. P. Ward, W. A. Judy, K. W. Scott, J. Am. Chem. Soc., 1968,,90, 4133
J. L. Herisson, Y. Chauvin Makromol. Chemie, 1971, 141, 162
 Olefin Metathesis - Mechanism
1975 Grubbs Deuterium Labelling experiment

R. H. Grubbs, P. L. Burk and D. D. Carr, J. Am. Chem. Soc. 1975, 97,3265.

T. J. Katz and R. Rothchild, J. Am. Chem. Soc. 1976, 98,2519.
R.H. Grubbs, Nobel Lecture, 2005
Chauvin’s Mechanism
Chauvin’s Mechanism

Y. Chauvin, Nobel Lecture, 2005

Olefin Metathesis - Mechanism
Types of Olefin Metathesis
Ring Opening Metathesis Polymerization (ROMP)

•ROMP is thermodynamically favored for strained ring systems, such as 3-, 4-, 8- and larger-membered
compounds.

•When bridging groups are present (bicyclic olefins) the ΔG of polymerization is typically more negative
as a result of increased strain energy in the monomer.

•Block copolymers can be made by sequential addition of different monomers (a consequence of the
"living" nature of the polymerization).
 Ring Closing Metathesis (RCM)

The reaction can be driven to the right by the loss of ethylene.

• The development of well-defined metathesis catalysts that are tolerant of many functional groups yet
reactive toward a diverse array of olefinic substrates has led to the rapid acceptance of the RCM reaction as
a powerful method for forming carbon-carbon double bonds and for macrocyclizations.

• Where the thermodynamics of the closure reaction are unfavorable, polymerization of the substrate can
occur. This partitioning is sensitive to substrate, catalyst, and reaction conditions.
 Cross Metathesis (CM)

Self-dimerization reactions of the more valuable alkene may be minimized by the use of an excess of the more
readily available alkene.

Acyclic Diolefin Metathesis (ADMET)

Ring Opening Cross Metathesis (ROCM)

 Prerequisites for Good ROMP Catalysts

• Well-defined
• Initiation faster than propagation
• Limits chain transfer and termination
• Soluble in organic media
• Show high stability to moisture, air,temperature, and a variety of organic
functional groups

C.W. Bielawski, R.H. Grubbs Prog. Polym. Sci. 32 (2007) 1.

ROMP Mechanism
 Let’s get to Know who are the ”Catalysts”

1975 First well-defined Olefin Metathesis Catalyst

developed by Thomas J. Katz

Katz proposed that the presence of a Carbene on the catalyst would

facilitate the reactivity
 Titanium Tantalum
• Higher activity than Titanium
• Isolable Metallacyclobutane
• Reactive with heteroatoms
• Catalyzes ROMP of Norbornene with good MW
• Catalyst tailoring
control, PDI ∼1.2
- The bulky, electron rich aryloxides decreased
• Reactivity heteroatom
side reactions
- PDI ∼ 1.1 with bulky as opposed to PDI ∼1.6
with less bulky groups for ROMP of
Norbornene
Basset’s Tungsten Catalyst
• wider functional group tolerance (acetates, nitriles,
anhydrides)
• bulky alkoxide ligands show stereoselectivity
• high activity, increased side reactions

Schrok’s Imido-alkoxy Catalyst

• alkoxide varied to moderate activity

• limited functional group tolerance
 Schrok’s Imido-alkoxy Catalyst
• Molybdenum alkylidenes, well-defined
• Highly active
• Good functional group tolerance
- ester, amide, imide, ketal, ether, cyano, trifluoromethyl and
primary halogens.
• Must be used in inert conditions, no water
• Stereochemical control through alkoxy ligands