Organometallic Compounds:

“Organometallic compound, any member of a class of substances containing at least one metal-
to-carbon bond in which the carbon is part of an organic group.”
o Organometallic compounds constitute a very large group of substances that have played a
major role in the development of the science of chemistry.
o They are used to a large extent as catalysts (substances that increase the rate of reactions
without themselves being consumed) and as intermediates in the
laboratory and in industry.

Example:

The class includes such compounds as ferrocene, a remarkably

stable compound in which an iron atom is sandwiched between
two hydrocarbon rings.

History:
The first synthetic organometallic compound, K[PtCl3(C2H4)], was
prepared by the Danish pharmacist William C. Zeise in 1827 and is often
referred to as Zeise’s salt.

Applications of Organometallic Compounds:

Organometallic compounds have a broad spectrum of applications in various fields:

• Catalysis: They are essential in catalysis, particularly in processes like hydrogenation,

hydroformylation, and polymerization. For example, Ziegler-Natta catalysts, which are
organometallic compounds, are used in the polymerization of olefins.

• Synthesis: Organometallics are used in organic synthesis to form carbon-carbon and

carbon-heteroatom bonds. Grignard reagents, for instance, are crucial in forming alcohols,
carboxylic acids, and other organic molecules.

• Material Science: They play a role in the development of materials such as

semiconductors, superconductors, and nanomaterials.

• Medicine: Some organometallic compounds have therapeutic applications. Cisplatin, a

platinum-based compound, is widely used in cancer treatment.

A new approach involves modeling of both pharmacological and catalysis properties of established
drugs with organometallic fragments for clinical and industrial purposes, several metal complexes
have been tested in anticancer therapy, the development of metal complexes with platinum central
atoms such as cisplatin, carboplatin and oxaliplatin had an enormous
impact on current cancer chemotherapy (Fig 6).

In particular, cisplatin has become one of the most widely used drugs and
is highly effective in treating several cancers such as ovarian and testicular
cancers (Meng et al, 2009).

🏭 Industrial Applications:
Organometallic compounds are widely used both stoichiochemically in research and industrial
chemical reactions, as well as in the role of catalyst to increase the rate of such reactions (e.g., as
in the uses of homogeneous catalysis), where target molecules include polymers, pharmaceuticals,
and many other types of practical products.
For instance, organolithium, organomagnesium, and organoaluminium compounds, examples of
which are highly basic and highly reducing, are useful stoichiometrically, but also catalyze many
polymerization reactions.
Almost all processes involving carbon monoxide rely on catalysts, notable examples being
described as carbonylation. The production of acetic acid from methanol and carbon monoxide is
catalyzed via metal carbonyl complexes in the Monsanto process and Cativa process.
Most synthetic aldehydes are produced via hydroformylation. The bulk of the synthetic alcohol, at
least those larger than ethanol, are produced by hydrogenation of hydroformylation-derived
aldehydes. Similarly, the Wacker process is used in the oxidation of ethylene to acetaldehyde.

1. Bulk Chemical Production

Monsanto Process: (Carbonylation of Methanol)
The Monsanto process is an industrial method for the manufacture of acetic acid by
catalytic carbonylation of methanol.[1] The Monsanto process has largely been supplanted by
the Cativa process, a similar iridium-based process developed by BP Chemicals Ltd, which is
more economical and environmentally friendly. This process operates at a pressure of 30–
60 atm and a temperature of 150–200 °C and gives a selectivity greater than 99%. It was
developed in 1960 by the German chemical company BASF and improved by the Monsanto
Company in 1966, which introduced a new catalyst system.[2]

Catalyst: Rhodium complex, typically [Rh (CO)₂I₂] ⁻

🧪Mechanism:

1. Generation of Methyl Iodide:

CH3OH + HI → CH3I + H2O
 2. Oxidative Addition:
[Rh (CO)2I2 ]− + CH3I → [Rh (CH3) (CO)2I3]−
3. Migratory Insertion of CO:
[Rh (CH3) (CO)2I3]− + CO → [Rh (COCH3) (CO)I3]−
4. Reductive Elimination:
[Rh (COCH3)(CO)I3]− → CH3COI + [Rh(CO)2I2]−
5. Hydrolysis:
CH3COI + H2O → CH3COOH + HI
The overall cycle is:

Modern Replacement

The Monsanto process was largely replaced by the Cativa process, developed by BP Chemicals
in the 1990s. The Cativa process uses an iridium-based catalyst, offering:

• Better catalyst stability

• Higher efficiency

• Lower environmental impact

2. Petrochemical Processing
Olefin metathesis:
Olefin metathesis is a popular and useful reaction. In the presence of certain transition-metal
compounds, including various metal carbenes, olefins exchange the groups around the double
bonds, resulting in several outcomes: straight swapping of groups between two acyclic olefins
(cross-metathesis), closure of large rings (ring-closing metathesis), formation of dienes from
cyclic and acyclic olefins (ring-opening metathesis), polymerization of cyclic olefins (ring-
opening metathesis polymerization), and polymerization of acyclic dienes (acyclic diene
metathesis polymerization).
This reaction was first used in petroleum reformation for the synthesis of higher olefins
(Shell higher olefin process - SHOP), with nickel catalysts under high pressure and high
temperatures. Nowadays, even polyenes with MW > 250,000 are produced industrially in
this way.
Catalyst: The homogeneous catalysts are often classified as Schrock catalysts and Grubbs
catalysts. Schrock catalysts feature molybdenum(VI)- and tungsten(VI)-based centers supported
by alkoxide and imido ligands.[4]

Grubbs catalysts, on the other hand, are ruthenium(II) carbenoid complexes.[5] Many variations of
Grubbs catalysts are known. Some have been modified with
a chelating isopropoxybenzylidene ligand to form the related Hoveyda–Grubbs catalyst.

Ring-Closing Olefin Metathesis (RCM):

Ring-Closing Metathesis (RCM) is a type of olefin metathesis reaction where a diene (a molecule
with two terminal alkenes) undergoes intramolecular metathesis to form a cyclic alkene and often
ethylene as a by-product.

General Reaction

CH2=CH–(CH2)n–CH=CH2 → [M]=CHR Cyclic Alkene + CH2=CH2

RCM Mechanism
1. Catalyst Activation

The precatalyst (like Grubbs) generates an active metal-carbene complex:

 [M]=CH Ph(or other alkylidene group)

2. First [2+2] Cycloaddition

The metal-carbene reacts with one of the terminal alkenes of the diene:
[M]=CHPh + CH2=CH–(CH2) n–CH=CH2 → Metallacyclobutane Intermediate A

3. Cycloreversion

Breaks the metallacyclobutane to form:

• A new internal alkene (part of the ring)
• A new metal-carbene
Metallacyclobutane A → [M]=CH–(CH2)n–CH=CH2 + CH2=CHPh
The new metal-carbene is still active and can now react intramolecularly.

4. Second [2+2] Cycloaddition

The new metal-carbene reacts within the same molecule, with the second terminal alkene:
[M]=CH–(CH2)n–CH=CH2 → Metallacyclobutane Intermediate B

5. Final Cycloreversion

• Forms the cyclic alkene (the ring-closed product)

• Releases ethylene as a byproduct
• Regenerates the original metal-carbene catalyst
Metallacyclobutane B → Cyclic Alkene + CH2=CH2
The overall cycle is:
 Advantages in Industry
Advantage Description

Atom Economy Minimal by-products (mainly ethylene)

Functional Group
Especially with Ru catalysts
Tolerance

Mild Conditions Room temp to moderate heating

Works for small molecules, polymers, and bio-based

Versatility
feedstocks

3. Fine Chemicals & Pharmaceuticals

➤ Cross-Coupling Reactions
• Metals: Pd, Ni, Cu
• Reactions: Suzuki, Heck, Stille, Sonogashira
• Use: Drug synthesis, agrochemicals, dye intermediates
➢ Here we will explain Suzuki coupling reaction.

Suzuki-Miyaura coupling
Suzuki-Miyaura coupling (or Suzuki coupling) is a metal catalyzed reaction, typically with Pd,
between an alkenyl (vinyl), aryl, or alkynyl organoborane (boronic acid or boronic ester, or special
cases with aryl trifluoroborane) and halide or triflate under basic conditions.

General Reaction

Ar–X + Ar’–B(OH)2 Pd0,base Ar–Ar’ + BX(OH)

o Ar–X: aryl or vinyl halide (X = I, Br, sometimes Cl)
o Ar'–B(OH)₂: aryl or vinyl boronic acid
o Base: K₂CO₃, NaOH, etc.
o Catalyst: Pd(PPh₃)₄ or Pd(OAc)₂ with phosphine ligands
 Mechanism:
Step 1: Oxidative Addition

The Pd(0) catalyst adds into the C–X bond of the aryl halide:

Pd0 + Ar–X → Ar–Pd(II)–X

• Pd is oxidized from 0 to +2.

• Forms a square-planar palladium(II) complex.

Step 2: Transmetalation

The organoboron reagent (Ar′–B(OH)₂), activated by a base, transfers its aryl group to the
palladium complex:

Ar–Pd(II)–X + Ar’–B(OH)2 → BaseAr–Pd(II)–Ar’+BX(OH)

• Base helps form the reactive boronate intermediate.

• X (halide) is replaced by Ar′.

Step 3: Reductive Elimination

The two aryl groups on palladium couple, releasing the biaryl product and regenerating Pd(0):

Ar–Pd(II)–Ar’ → Ar–Ar’ + Pd0

• Pd is reduced from +2 back to 0.

• This completes the catalytic cycle.
The overall cycle is:

Applications:
 • Synthesis of biaryl drugs (e.g., Valsartan, Losartan)

• Conjugated materials for OLEDs and solar cells

• Liquid crystals and specialty chemicals

4. Hydroformylation (Oxo Process)

Hydroformylation, also known as oxo synthesis, is a chemical reaction involving the addition of
carbon monoxide (CO) and hydrogen (H₂) to an unsaturated compound, typically an alkene or
alkyne. The reaction is catalyzed by transition metal complexes, such as rhodium or cobalt,
leading to the formation of aldehydes or aldehyde derivatives.

Catalyst: Cobalt-based catalysts:

• Example: HCo(CO)₄

• Conditions: High temperature (150–200°C) and pressure (100–300 atm)

• Pros: Simple, well-understood

• Cons: Harsh conditions, less selective

Rhodium-based catalysts (more modern):

• Example: HRh(CO)(PPh₃)₃

• Conditions: Milder temperature and pressure (40–120°C, 10–50 atm)

• Pros: High selectivity, operates under milder conditions

• Cons: More expensive

Here reaction will be explained by using Rhodium based catalyst.

General Reaction:

RCH=CH2 + CO + H2 Catalyst
RCH2CH2CHO (linear) + RCH(CH3)CHO (branched)

• Reactants: Alkene, carbon monoxide (CO), hydrogen (H₂)

• Products: Mixture of linear and branched aldehydes

Mechanism of Rhodium-Catalyzed Hydroformylation (Oxo Process)

Step 1: Catalyst Activation

The pre-catalyst HRh(CO)(PPh₃)₃ undergoes ligand dissociation:

HRh(CO)(PPh3)3 → HRh(CO)(PPh3)2 + PPh3

 • This forms the active 14-electron complex, which is coordinatively unsaturated and
ready to bind the alkene.

Step 2: Alkene Coordination

An alkene (e.g., propene) coordinates to the rhodium center:

HRh(CO)(PPh3)2 + CH2=CHCH3 → Alkene-Rh complex

Step 3: Migratory Insertion (Alkene into Rh–H Bond)

The coordinated alkene inserts into the Rh–H bond:

Rh–H + CH2=CHCH3 Rh–CH2CH2CH3

• This step forms an alkyl–rhodium complex.

Step 4: Carbon Monoxide Coordination

CO binds to the metal center:

Rh–CH2CH2CH3 + CO Rh(CO)–CH2CH2CH3

Step 5: Migratory Insertion of CO

The CO ligand inserts into the Rh–C bond to form an acyl–rhodium complex:

Rh(CO)–CH2CH2CH3 Rh–COCH2CH2CH3

Step 6: Oxidative Addition of H₂

Hydrogen (H₂) adds across the Rh center:

Rh–COCH2CH2CH3 + H2 Rh(H)2–COCH2CH2CH3

Step 7: Reductive Elimination

Reductive elimination gives the aldehyde product (e.g., butyraldehyde) and regenerates the
catalyst:

Rh(H)2–COCH2CH2CH3 CH3CH2CH2CHO + {HRh(CO)(PPh3)}2

The overall cycle is:

Industrial Applications:
The Oxo process is a cornerstone of industrial organic chemistry, bridging basic hydrocarbons
and high-value chemicals. Its role in the production of aldehydes and alcohols is essential for:

• Plasticizers

• Surfactants

• Lubricants

• Agrochemical and pharmaceutical synthesis

5. Catalysis in Petrochemical and Chemical Industries

Organometallic compounds serve as highly efficient homogeneous and heterogeneous catalysts in
many key industrial processes.

Hydrosilylation:
Hydrosilylation, also known as hydrosilation, is one of the most useful catalytic reactions leading
to the formation of organsilanes and organosilicones, which have a variety of applications in
industry and as intermediates in organic chemistry. Hydrosilylation occurs via the addition of H-
Si to an unsaturated bond such as carbon-carbon bond, carbon-oxygen bond, carbon-nitrogen
bond, nitrogen-nitrogen bond and nitrogen-oxygen bond using a metal catalyst, Lewis Acid, or
radical initiator.
The process is widely applied in industry to produce silane coupling agents and silicone polymers
such as oils, rubbers and resins.1 The hydrosilylation reactions can also produce various
organosilicon reagents, which are used in fine chemical synthesis for stereospecific oxidation,
cross-coupling reactions, etc.2–4

Most Used Catalysts:

• Speier’s catalyst: H₂PtCl₆ in isopropanol

 • Karstedt’s catalyst: Pt(0) complex with vinylsiloxane ligands — widely used in industry for
silicones

General Reaction

R2C=CR2 + H–SiR’3 Catalyst

R2CH–CR2SiR’3

Mechanism – Chalk–Harrod Pathway (Pt-catalyzed)

This is the most accepted mechanism for Pt-catalyzed hydrosilylation.

Step 1: Oxidative Addition of Si–H

Pt0 + H–SiR’3 ⟶ Pt(II)–H–SiR’3

• Metal inserts into Si–H bond

Step 2: Alkene Coordination

Pt(II)–H–SiR’3 + R₂C=CR₂ ⟶ Pt–alkene complex

Step 3: Migratory Insertion (Hydride Transfer)

Pt–H + C=C ⟶ Pt–alkyl

• Hydride adds to one carbon of the double bond (usually anti-Markovnikov)

Step 4: Reductive Elimination

Pt–alkyl–SiR’3 ⟶ R₂CH–CR₂SiR’3 + Pt(0)

• Forms the Si–C bond and regenerates the catalyst

The overall cycle is:
 Industrial Applications
1. Silicone production: Siloxane polymers made from organosilanes

2. Adhesives & Sealants: Crosslinking of silicone resins

3. Coatings: Functionalization of surfaces (glass, metals)

4. Biomedical materials: Hydrophobic drug carriers, bioactive surfaces

5. Microelectronics: Modification of semiconductor surfaces

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