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Termpaper 221

The document discusses various organometallic catalysts including Wilkinson's catalyst for hydrogenation, Grubbs' catalyst for olefin metathesis, the Monsanto catalyst for acetic acid production, SHOP catalyst for linear alpha-olefins, and Ziegler-Natta catalyst for polymerization of alkenes. Each catalyst is described in terms of its structure, mechanism, industrial applications, and limitations. The document highlights the significance of these catalysts in chemical processes and their contributions to the field of organometallic chemistry.

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0 views8 pages

Termpaper 221

The document discusses various organometallic catalysts including Wilkinson's catalyst for hydrogenation, Grubbs' catalyst for olefin metathesis, the Monsanto catalyst for acetic acid production, SHOP catalyst for linear alpha-olefins, and Ziegler-Natta catalyst for polymerization of alkenes. Each catalyst is described in terms of its structure, mechanism, industrial applications, and limitations. The document highlights the significance of these catalysts in chemical processes and their contributions to the field of organometallic chemistry.

Uploaded by

Sam Rajput
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Organometallic chemistry

Term paper 2

Name : Manish

Entry No. 2024CYS7005

1. Willikinsons Catalyst

Wilkinson’s catalyst, [RhCl(PPh₃)₃], is a well-known homogeneous catalyst used primarily


for the hydrogenation of alkenes. It was discovered by Sir Geoffrey Wilkinson and is highly
selective for terminal and internal alkenes, operating under mild conditions [1]. Wilkinson’s
catalyst has a square planar geometry with Rh(I) as the central metal. Its formula is
[RhCl(PPh₃)₃], where:

 Rh(I) is the active metal center.


 Three triphenylphosphine (PPh₃) ligands stabilize the metal center.
 Chloride ion (Cl⁻) acts as an ancillary ligand
 Wilkinson’s catalyst is synthesized by reacting rhodium(III) chloride hydrate with
triphenylphosphine (PPh₃) in ethanol.[1]

3. Mechanism of Catalysis (Hydrogenation of Alkenes) [2]

 Dissociation of PPh₃ which Reduces steric bulk and one solvent molecule bonds to it
Generates active Rh(I) species.

 Oxidative addition of H₂ to active catalyst takes place molecule and Rh(I) to Rh(III).

 Alkene binds to catalyst then solvent molecule leaves the complex and Activates the
substrate.

 Migratory insertion → First H⁻ transfer to alkene.and make it saturated and sigma bond is
formed between substrate and metal catalyst

 Reductive elimination of alkyl and migrated hydrogen takes place leading to Alkane
formation, catalyst regeneration.
2. Grubbs catalyst

Grubbs’ catalyst is a ruthenium-based complex widely used in olefin metathesis, a


powerful reaction for forming carbon-carbon double bonds. It was developed by
Robert H. Grubbs, earning him the 2005 Nobel Prize in Chemistry.[3]

1.Structures and properties

Grubbs’ catalyst has the general formula [RuCl₂(=CHPh)(PR₃)₂], where:

 Ru (Ruthenium) is the central metal.


 Two chloride ligands (Cl₂) provide stability.
 One alkylidene (benzylidene) ligand initiates metathesis.
 Two phosphine (or NHC) ligands tune reactivity. [3]

2.Two major generations exist:

 First-generation Grubbs Catalyst: Uses PCy₃ (tricyclohexylphosphine) ligands.


 Second-generation Grubbs Catalyst: Uses NHC (N-heterocyclic carbene) ligands,
increasing stability and activity.
3. Functions of Grubbs catalyst

Grubbs’ catalyst is primarily used in olefin metathesis, which involves the exchange of
alkene fragments to form new double bonds. Key applications include:

 Ring-Closing Metathesis (RCM): Forms cyclic alkenes.


 Ring-Opening Metathesis Polymerization (ROMP): Used in polymer synthesis.
 Cross Metathesis (CM): Joins two different alkenes.[4]

4. Mechanism and synthesis

[4]

3.Monosanto Catalyst

The Monsanto catalyst is a rhodium-based homogeneous catalyst used in the


Monsanto process, which efficiently produces acetic acid from methanol via
carbonylation. This catalyst was historically significant but has been largely replaced
by the Cativa process (iridium-based catalyst) for industrial acetic acid
production.[5]

1. Structure and Composition

The active catalyst in the Monsanto process is cis-[Rh(CO)₂I₂]⁻, which forms in solution
from:

 Rhodium(III) iodide (RhI₃) or rhodium(II) acetate.


 Methyl iodide (CH₃I) as a promoter.
 Carbon monoxide (CO) as the reactant.

2. Industrial Importance
 The Monsanto process was widely used for acetic acid production due to its high
efficiency and selectivity.
 It operates under mild conditions (150-200°C, 30-60 atm CO pressure).
 However, rhodium is expensive, and the Cativa process (Ir-based catalyst) has
largely replaced it due to better efficiency and catalyst stability.[6]

3.Synthesis and mechanism

Complex:

2. Carbonylation to Active Catalyst:

[6]

4. Shop catalyst (Nickel phosphine complex)

he SHOP (Shell Higher Olefin Process) catalyst is a crucial component in the industrial production
of linear alpha-olefins (LAOs) from ethylene via oligomerization. This catalyst system primarily
consists of nickel-based complexes supported by phosphorus ligands.[7]

Key Features of the SHOP Catalyst:

1. Active Metal: Nickel (Ni) in a coordination complex.


2. Ligands: Phosphine-based ligands such as tertiary phosphine and chelating
phosphanylenolato ligands
3. Nickel in (+2) oxidation state, square planar complex
4. Reaction Type: Ethylene oligomerization, selectively producing even-numbered alpha-
olefins (C₄ to C₁₈+). [7]

Industrial use and Limitation

o Produces even-numbered C₄–C₁₈+ olefins, essential for industrial applications.


o Used in the manufacture of plastics, synthetic lubricants, and detergents
o LAOs from SHOP are further processed into polyethylene co-monomers,
plasticizers, and oil additives.
o Requires additional separation steps, increasing cost and complexity.
o Nickel catalysts are prone to deactivation due to poisoning by sulfur
compounds.[8]

Mechanism

[8]

5. Zeigler natta catalyst

The Ziegler-Natta catalyst is a highly effective catalyst system used in the


polymerization of olefins (alkenes), such as ethylene and propylene, to produce
polyethylene (PE) and polypropylene (PP). It was developed by Karl Ziegler
and Giulio Natta, earning them the 1963 Nobel Prize in Chemistry.[9]

1.KEY POINTS
 Transition Metal Compound (Catalyst):
o Typically Titanium (Ti) in the form of Titanium Tetrachloride (TiCl₄) or
Titanium Trichloride (TiCl₃).
 Alkylaluminum Compound (Co-Catalyst):
o Trialkylaluminum (AlR₃), such as Triethylaluminum (Al(C₂H₅)₃).

2.Industrial use and Limitation

1.The Ziegler-Natta catalyst is primarily used for the polymerization of alkenes


(olefins) to produce high-molecular-weight polymers like polyethylene (PE)
and polypropylene [9]

2. Its function is based on coordination polymerization, which involves


controlling monomer insertion into a growing polymer chain.

3.Low Stereoselectivity While isotactic polypropylene can be produced,


controlling syndiotactic and highly uniform polymer structures is challenging.

4.The catalyst gradually deactivates due to side reactions or impurities in


monomers. Moisture & Oxygen Sensitivity:

3. Synthesis

TiCl4 + Al(C2H5)3 --> Catalyst complex

4.Mechanism

Mechanism of Polymerization[10]

1. Alkene Coordination → The alkene binds to the titanium center.


2. Insertion into Ti–C bond → Monomer inserts between Ti and growing polymer
chain.
3. Chain Growth → Repeated monomer addition leads to polymer formation.
References

1. 1.J. Am. Chem. Soc. 1977, 99, 15, 5217–5218


2. Williamson, D. H. (1976). "Homogeneous Hydrogenation Catalysts in Organic
Synthesis".
3. Grubbs, R. H.; Trnka, T. M. (2004). "Ruthenium-Catalyzed Olefin Metathesis". In
Murahashi
4. 4.Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. (1999). "Synthesis and Activity of a
New Generation of Ruthenium-Based Olefin Metathesis
5. 5.Cavit, B. E., & Cole-Hamilton, D. J. (2001). Mechanistic studies of the Monsanto
acetic acid process.
6. Moulijn, J. A., van Leeuwen, P. W. N. M., van Santen, R. A. (2001). Catalysis
7. 7.Mol, J. C. (2004). "Industrial applications of olefin metathesis". Journal of
Molecular Catalysis A: Chemical
8. 8.Gadi Rothenberg (17 March 2008). Catalysis: Concepts and Green Applications
9. Hoff, Ray; Mathers, Robert T., eds. (2010). Handbook of Transition Metal
Polymerization Catalysts
10. 10.Giuliano Cecchin; Giampiero Morini; Fabrizio Piemontesi (2003). "Ziegler–Natta
Catalysts"

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