ORGANO-METALLIC CHEMISTRY

WHAT IS ORGANO-METALLIC CHEMISTRY?

HOW STRONG IS THE METAL-ORGANIC BOND?

HOW IS IT DIFFERENT FROM THE COORDINATION CHEMISTRY THAT

YOU STUDIED RECENTLY?

CAN THE METAL-CYANIDE COMPLEXES BE CLASSIFIED UNDER

ORGANOMETALLICS?

ARE THE METAL HYDRIDES BEING COVERED UNDER

ORGANOMETALLIC CHEMISTRY?
 ORGANO-METALLIC CHEMISTRY: Historical Background

First organometallic compound [PtCl2(CO)2] by W.C. Zeise in 1827.

40 years later, [PtCl2(CO)]2 reported by P. Schutzenberger.

Next one was Ni(CO)4, by L. Mond, C. Langer & F. Quinke in 1890.

By 1900, the Metal-carbonyl syntheses were reasonably developed.

1930s, W. Hieber reported metal carbonyl clusters: [Fe4(CO)13]2-. Extremely difficult to

characterize at that time.

When advance techniques such as IR, NMR & X-ray diffraction started coming into existence,
then these could be characterized 1950 onwards.
 METALLOCENES (Why these are so important? Why Nobel prize?)

Ferrocene, Fe(C5H5)2 was synthesized accidentally (unplanned): 1951 by Peter L. Pauson and
Thomas J. Kealy

Fischer & Wilkinson got

Wrong Structure by Pauson, 1951 Nobel Prize in 1973
Woodward & Wilkinson, 1952

Even the 4d, 5d & also lanthanide metallocenes are known today.
Diversity in Metal – Carbon Bonds
 Nature of the organometallic compounds?
Unlike the classical coordination compounds,
these resemble mostly the organic compounds in terms of their solubility, low melting,
crystallisability, etc.
These are generally 16 & 18 electron compounds.
The ligands bound in the complex undergo variety of reactions: Example of Grignard
Reagent (RMgX).
The organic moiety
present in it is activated
& made ready for
reactions of all kinds.
 Nature of the organometallic compounds?
Uses: industrial catalysis; pharmaceutical industry; organic synthesis
Electronegativity difference between C & M and
% of ionic character
 How strong is the M-C bond?
100 to 250 kJ/mol in 3d-complexes
M-C Strength: sp > sp2 > sp3
M-C Strength increases from left to right (in a period) &
Decreases top to bottom (in a group) in the d-block elements
In Metal – carbonyls, the M-C bond strength increases as a function of increase in the
back-bonding
M-R: methyl > ethyl > propyl > iso-propyl
The more the crowd on the carbon attached, the weaker the
M-C bond is.
Thus the M-C strength depends on both the ionic contribution of M-C bond & the
steric or repulsive effect from the bonded carbon.
So, the strength also depends on the electronegativity difference between the C & M.
 Common reactions of Organometallic Compounds
A. Reactions involving gain or loss of the ligands
(1)Ligand dissociation and substitution
(2)Oxidative addition
(3)Reductive elimination
(4)Nucleophilic displacement
B. Reactions involving modification of ligands
(1)Insertion
(2)Migration
(3)Hydride elimination
(4)Abstraction
(5)A combination of some of these
Common reactions of Organometallic Compounds
 Oxidative Addition (OA)

Concerted Process

The coord. number increases by 2

(X-Y = H-H, H-X, R-X, Ar-X, R-H, R-R)
Most common for d8 & d10 metals: SN2 – Type process:
Rh(0), Os(0), Rh(I), Pd(0), Pt(0), Pt(II)

SN2 – type: via bimolecular nucleophilic substitution.

Nucleophillic attack by the metal center at the less
electronegative atom in the substrate leads to cleavage of
the R–X bond, to form an [M–R]+ species. This step is
followed by rapid co-ordination of the anion to the cationic
metal center.
 Reductive Elimination (RE)
The oxidation state of M decreases by 2
The coordn. number is decreased by 2
RE is favoured for the complexes that are:
(i) The newly formed X-Y bond should be strong.
(ii) The X & Y should be mutually adjacent in the coordination sphere
(iii) The X & Y should be more electronegative than M
(iv) Sterically hindered (bulky ligands) will favour RE
(v) Electronically poor: (vi)d6  Pd(IV), Pt(IV),
high OS metals; Rh(III) & Ir(III)
poor Donor ligands; (vii) d8  Ni(II), Pd(II), Au(III)
+ively charged complexes
 Reactivity of Organometallic Compounds
Ligand substitution: Associative & Dissociative

Ligand substitution: The reactivity is more like that in case of coordination compounds.
(i) The valence electron count at the metal atom does not increase above 18;
(ii) Steric crowding of ligands increases the rate of dissociative processes and decreases the rate of
associative processes.

Cr(CO)6 + sol → Cr(CO)5(sol) + CO

Cr(CO)5(sol) + L → Cr(CO)5L + sol (dissociate type)

The 16e complexes generally goes through associative type. Eg. Below:
[Ir(CO)Cl(PPh3)2] + PEt3 → [Ir(CO)Cl(PPh3)2(PEt3)] → [Ir(CO)Cl(PPh3)(PEt3)] +PPh3

[V(CO)5(NO)]+PPh3  [V(CO)5(NO)(PPh3)] [V(CO)4(NO)(PPh3)]+CO

 Reactivity of Organometallic Compounds
Both OA & RE sequentially
-Bond metathesis: A reaction sequence that appears to be an oxidative addition (OA) followed by a
reductive elimination (RE) may in fact be the exchange of two species by a process known as -bond
metathesis.
This is most common with lanthanides and actinides.
 Reactivity of Organometallic Compounds
Migratory insertion reactions result
from the migration of a species such
as a hydride or alkyl group to an
adjacent ligand such as carbonyl to
give a metal complex with two fewer
electrons on the metal atom.

Ligands which favour migratory insertion are:

Anionic: H-, R- (alkyl), Ar- (aryl), acyl-, O2- (oxo)
Neutral: CO, alkenes, alkynes, carbenes
 Reactivity of Organometallic Compounds
1,2-Insertions: 1,2-Insertion reactions are observed with 2-ligands such as alkenes and results in the
formation of an 1 -ligand with no change in the oxidation state of the metal;
–hydride elimination: -hydride elimination is the reverse of 1,2-insertion.

Its reverse reaction is

Hydride elimination
 Reactivity of Organometallic Compounds
-,  -, and -Hydride eliminations and cyclometallations: Cyclometallation reactions, in which
a metal inserts into a remote CH bond, are equivalent to hydride elimination reactions, this leads to
cyclization.
 Tutorial VIII: Organometallic Chemistry
Identify and or classify the following reactions under different categories, such as, Oxidative addition,
Reductive Elimination, ligand dissociation/substitution, insertion/migratory insertion, elimination, ligand
coordination
Tutorial VIII: Organometallic Chemistry
Identify and or classify the
following reactions under
different categories, such as,
Oxidative addition, Reductive
Elimination, ligand dissociation/
substitution, insertion/migratory
insertion, elimination, ligand
coordination, etc.
 Tutorial VIII: Organometallic Chemistry
Identify and or classify the following reactions under different categories, such as, Oxidative addition,
Reductive Elimination, ligand dissociation/substitution, insertion/migratory insertion, elimination, ligand
coordination.
Further questions, comments & discussions please!
 Catalysts & Catalysis
Catalysis plays vital roles in the production of food, fuel, commodity
chemicals, fine chemicals and pharmaceuticals
More than 60% of all chemical products and 90% of all the chemical
processes are based on catalysis
A whole new technology appeared based on Organometallic catalysis in
olefin polymerization
Nobel prizes for chemistry have been awarded to Zieglar and Natta (1963),
Fischer and Wilkinson (1973) for their discoveries in organometallic
chemistry and homogeneous catalysis.
Recently, in 2005, Chauvin, Schrock and Grubbs were awarded the Nobel
prize for developing organometallic catalysts for olefin metathesis.
A catalysed reaction is faster and is more specific than the corresponding un-
catalysed one.
 Catalyst & Catalysis
The key substance or compound in the catalysis is known as catalyst. The
catalyst increases the rate of the reaction but is not self consumed in the
reaction, because the catalyst provides a different pathway with lowering the
activation energy.
The catalyst efficiency is measured as “Turnover Frequency”.
Turnover Frequency: Is also known as Turnover Number, N and is defined as
molecules reacting per active site in unit time. [OR] The number of moles of
substrate that a mole of catalyst can convert before becoming inactivated.
This can be obtained as the rate of the reaction over the catalyst
concentration.
An ideal catalyst should have an infinite turnover number in this sense,
because it would never be consumed. In actual practice, these range from 100
to 1000000 or more.
 Catalyst & Catalysis
A highly active catalyst results in high rates of reaction even at low
concentrations of the catalyst and end up with showing high turnover
frequency.
It will be selective by producing no or minimal quantity of side product,
hence important in industries owing to the cost factor and adding not
much to the pollution.
Small amount catalyst should come for large number of cycles.
The catalyst though not consumed in the process, often destroyed by the
side reactions
E.g., several alkene polymerization catalysts are destroyed by O2, hence
the reactions are conducted in O2 excluded environment.
Catalysis can be one of the two types: Homogeneous & Heterogeneous
 Homogeneous & Heterogenous Catalysis
Homogenous Heterogeneous
Form Soluble metal Metals, usually
complexes supported on oxides
Phase Liquid Solid/liquid; solid/gas
(Solution)
Temperature Low (<250 C) High (250-500 C)
Activity Moderate High
Selectivity High Low
Diffusion Facile Can be very important
Heat Transfer Facile Can be problematic
Product Separation Difficult Facile
Catalytic Recycle Expensive Simple
Reaction mechanism Reasonably well Poorly understood
understood
Economic Impact Low to Very high
moderate
 Hydrogenation of Alkenes by Wilkinson’s Catalyst
Nobel prize in 1973
[RhCl(PPh3)3 and related complexes are used for the hydrogenation of a wide variety of alkenes at around 1
atm. Or less. The hydrogenation is highly sensitive to the phosphine ligand and the alkene substrate. The
corresponding alkyl phosphine ligands are inactive because they are strongly bound to the metal and do not
readily dissociate.
These reactions are used in the production of petro-
chemicals, fine chemicals used in pharmaceuticals, etc.

Suitable chiral ligands

can lead to enantio-
selective hydrogenations.
An enantioselective
hydrogenation catalyst
containing a chiral
phosphine ligand
referred to as DiPAMP
(4) is used to synthesize
L-Dopa (5), a chiral
amino acid used to treat
Parkinson’s disease.
 Hydroformylation or hydrocarbonylation Reactions
Co & Rh complexes are used for hydroformylation. The mechanism of hydroformylation reaction is
thought to involve a pre-equilibrium in which octacarbonyldiCo(0) [Co2(CO)8] combines with hydrogen at
high pressure to give a monometallic species that brings about the actual hydro-carbonylation.
[Co2(CO)8] + H2  2[Co(CO)4H]
[Co(CO)4H] (A)  [Co(CO)3H] (B) + CO
Aldehydes produced by hydroformylation
reactions are normally reduced to alcohols that
are used as solvents, plasticizers and in the
synthesis of detergents.
The scale of production is generally in millions of
tons per year.
In the presence of CO at
high pressure, (D) undergoes
migratory insertion and
coordinates another CO,
yielding acyl complex (E).

The Rh based catalyst for this is: A trigonal

bipyramidal complex, [Rh(CO)(H)(PPh3)3]
 Wacker oxidation of alkenes – Need for a co-catalyst
This is currently not in use in the
industry. But we will study this
because of its mechanistic interest.

The Wacker process is used to produce acetaldehyde from

ethylene and oxygen.
The most successful system uses a Pd(II) catalyst to oxidize
the alkene.
The Pd(0) thus formed in the reaction needs to be re-oxidized
to Pd(II) in order to resume the next cycle, i.e., to turn out to
be catalytic. For this Cu(II) salt is being used as a secondary
catalyst.
Similar catalysis is not possible with a Pt(II) complex. The
principal reason for the Pd(II) catalyst’s success is due to its
greater lability of Pd(II) (a 4d element) as compared to the
Pt(II), which is a 5d counterpart.
Further the oxidation of Pd(0)  Pd(II) is more favourable
than the corresponding Pt(0) Pt(II) couple.
 Tutorial IX: Catalyst & Catalysis
1. What are the important features of a catalyst?
2. How does one gauge the potential of a catalyst?
3. Among the homogeneous and heterogenous catalysis, which one you think is
more advantageous and beneficial & why
4. In general, how does one tune stereo (enantio) selectivity, into the products
prepared from homogenous catalysis?
5. In general, how does one realise or establish the mechanism for a catalytic
process?
6. In establishing the mechanism, which one among the homogenous and
heterogeneous catalysis is easier and why?
7. In general, what nature of the steps involved in the organometallic based
catalysis?
8. Why is that Pt(II) is not useful in the Walker oxidation of alkenes, while Pd(II)
is highly useful?
9. What is a co-catalyst and what is its role? You can explain by using an example.
 Tutorial IX: on Catalyst & Catalysis
Microscopic reversibility: If a certain series of steps (unit operations) constitutes the mechanism of a
forward reaction, the mechanism of the reverse reaction is given by the same steps but occurring backwards
(i.e., in reverse fashion).
Of course this will not be true for photochemical reactions.
The sequence of transition states and relative intermediates in the mechanism of a reversible reaction must
be the same but in reverse order for the backward reaction as per the forward reaction.
Further questions, comments & discussions please!