LECTURE 8: REACTION MECHANISM

General Mechanistic Principles Reactions

PROF. LYDIA W. NJENGA

Department of Chemistry
UON
INTRODUCTION TO REACTION MECHANISMS

• Organometallic compounds undergo relatively few different kinds of reactions

• The reaction mechanisms involved are:
i) Ligand substitution
ii) Oxidative addition
iii) Reductive elimination
iv) Migratory insertion
 Ligand Substitution
Both SN1 and SN2 type of mechanism will be considered (you have encountered them
already)

• ligand substitution: M-L + L’ → M-L’ + L

Ligand substitution can be associative, dissociative, or radical chain.

1. Dissociative:

This is an SN1 type of reaction and rate depends on [L] i.e [CO]. This produces 1st order
M(CO)6 ↔ M(CO)5 + L ↔ M(CO)5L +CO
Dissociative cont’d

• departing ligand leaves, and the incoming ligand enters the coordination sphere of the
metal to generate the product
• two-step pathway which corresponds to the SN1 reaction mechanism for organic
compounds. It is common for 18-electron complexes where coordinatively unsaturated 16-
electron intermediates are more likely.
 Contd
Associative An SN2 type; , the rate of reaction will depend on the Concentration of
both [L] and [M(CO)6]. This gives 2nd order and other factors
M(CO)6 + L ↔ L M(CO)6 ↔ M(CO)5 L + CO
• A 16e system is converted to 18e intermediate and finally 16e
• Incoming ligand will sit on equatorial site and the structure changes from square planar to
trigonal bipyramid
• Associative substitution is usually found with square planar d8 metal complexes such as
those of ir(II), Pd(II), Pt(II), Ir(I), and Au(III).
 Associative Cont’d

• Other factors: Nucleophilicity, (soft nucleophiles such as PR3 are particularly

effective when the metal center is soft acid[e.g, Pt(II)]),

• leaving group ability (a function of M−L bond strengthor Brønsted–Lowry

base strength; the weaker the base, the better the leaving group),
• The solvent, and
• the trans effect
 Contn’d
NOTE: Metal ions with the highest affinities for hard bases are hard acids whereas metal
ions with the highest affinity for soft bases are soft acids
Hard acids (Al3+, Mg2+), cations of electropositive metals and non-polarizable
Soft acids: Ag+ Pd2+, Pt2+, Hg2+cations of less electropositive metals; consequently, they
have lower charge-to-radius ratios and are more polarizable.
 Cont’d

• Interchange Mechanism

• Associative and dissociative reactions occurs simultaneously

MLnX + Y ↔ Y—MLn—X ↔ MLnY + X

 Oxidative Addition (OA)
• attachment of two groups X−Y to a metal complex of relatively low oxidation state
• The product will have two Oxidation state higher than the original
• Common X-Y reactants : H2, X2, C-X and C=C

Mononuclear oxidative cis-

addition. can also undergo
RE from (Ir(III) to Ir(I)
(Attribution: A. Vedernikov,
U Maryland (modified))
Cont’d

Mononuclear oxidative
coordination change from CN 4 to
CN 6

Dinuclear addition. Neither cis or trans

but Co-Co bond of dicobalt octacarbonyl
is broken and two HCo(CO) 4 formed
with H-Co(CO)4 no change in
Coordination
 Reductive Elimination (RE)
• RE is the opposite of OA :
• Oxidation number and electron count decreases
• Occurs when two group eliminated are in cis position eg:

Ref: Ruth Odhiambo SCH

404: course guide on
Organometallic Chemistry

The cis-orientation of the two hydrido

ligands is necessary to form an H-H
bond.
Ir-H bonds become larger while the H-
H bond become smaller leading to the
H2 molecule being eliminated
 Cont’d

• RE: also takes place in complexes with bulky ligands, electron deficient metals, high metal
oxidation state, strong Y-Z bond, high coordination number, and the presence
of groups that can stabilize the reduced metal fragment upon ligand loss (such as CO or
P(OR)3). eg
 Migratory Insertion
• Inserting molecule can act either as a nucleophile or as an electrophile to the metal
complex.
• coordination number and oxidation state of the metal remain unchanged
• Removal of the ligand is the one referred to as elimination
 Cont’d

• Carbonyl Insertion
• 1,1-insertion of carbon monoxide into a–alkyl (or aryl) bond.

Ref: Ruth Odhiambo SCH 404: course

guide on Organometallic Chemistry

Ref: Michael Evans

http://organometallicchem.files
 Cont’d

• Mechanisms : 3 different mechanisms

1.Carbonyl insertion
• Direct insertion of carbonyl to M-C bond
 Cont’d
2. CO migration
Formation of a 5- coordinate intermediate, with a vacant site available for
attachment of an incoming CO (18e-16e-18e)
 Cont’d
3. Alkyl migration:

Also produces a 5-coordinate complex and a vacant site available for the incoming
ligand. (18e-16e-18e)
“α”
Olefine Insertion

• The olefine insertion produces an alkyl group

• Below shows an olefine insertion and β-hydride elimination
• Referred as β- elimination because the H is attached to C in the alkyl chain 2nd to the metal
(“β”hydrogen)
• If H is attached to C attached to the M, it is referred to as “α” hydrogens
 Contn’d

• Hydroboration – already encountered

 INDUSTRIAL REACTIONS

Major industrial processes include

• hydrogenation, (Wilkinson’s catalyst, [RhCl(PPh3)3],

• hydrosilylation,
• hydrocyanation,
• olefin to acetydehyde (Wacker Process or Smidt Reaction- PdCl2/CuCl2) )
• carbonylation of methanol (cis [Rh (CO)2I2]) - based Monsato process Cartiva Process (Ir))
• alkene polymerization, (Titanium Catalyst - Ziegler-nata Catalysts)
• hydrocarboxylation, hydroformylation of alkene tto aldhyde (HCo(CO)4 or
[Rh(CO)H(PPh3)3 )
• Mainly involves catalysis
1. Homogeneous

2. Heterogeneous

Most of the reactions use homogeneous catalyst

 HYDROFORMYLATION ON ALKENES

• The mechanism of hydrocarbonylation is thought to involve a pre-equilibrium in which

Co2(CO)8 combines with hydrogen at high pressure to give a monometallic species that
brings about the actual hydrocarbonylation reaction
• discovered by Otto Roelen in 1938
• Also referred to as the oxo process or hydrocarbonylation, hydroformylation is a route to
producing an aldehyde from an alkene, hydrogen, and carbon monoxide.
• the production of aldehydes from alkenes (mainly butanal from propene. Also applied in:
• long-chain olefin or unsaturated alcohol.
• The process can also be called name is hydrocarbonylation.
• Main metals used are cobalt (Co) & Rhodium (Rh) = Rh was found by Wilkson to be a
thousand times more active than cobalt
Cont’d

MAIN POINT
• The mechanism of hydrocarbonylation is thought to involve a pre-
equilibrium in which octacarbonyldicobalt(0) combines with hydrogen at
high pressure to give a monometallic species that brings about the actual
hydrocarbonylation reaction
• Co2(CO)8 + RCH═CH2 + CO + H2 → RCH2CH2CHO + HCo(CO)3
 CONT’
Overall reaction: summarised by the following reaction
Main features of the mechanism RCH═CH2 + CO + H2 → RCH2CH2CHO
• Reaction is 1st order with respect to Olefin and
• б –bonding of olefins changing
to -bonding on Ligand. hydrogen inverse 1st order to the amount of CO
• Migration present.

• Carbonyl insertion • Rate is faster for terminal olefins than for internal
• Oxidative addition by olefin
hydrogen • Excess Carbonyl inhibits the reaction
• Elimination
Cont’d

• The effective low oxidation state catalyst is HCo(CO)4 which is produced from Co2(CO)8.
Co2(CO)8 + H2 ↔ 2 HCo(CO)4
HCo(CO)4 ↔ HCo(CO)3 + CO
HCo(CO)3 + CH2=CH2 → CH3CH2CHO
HCo(CO)3 is the effective homogeneous catalyst. To accept an olefine it must lose one carbonyl group.
Subsequently, the coordinated olefin is inserted into the Co-H bond and the resulting alkyls are
stabilized by the CO group.
Note the hydrogen can migrate to either of the 2 carbon atoms but the reaction is faster with terminal olefin
(CH2=CHCH3)
Hydroformylation is one of the most important processes in which a complex functions as a
catalyst
See below
Mechanism Of Cobalt-catalyzed Hydroformylation .
step 1, dissociation of CO from HCo(CO)4 to give the 16e
(HCo(CO)3)
step 2, Subsequent binding of alkene gives an 18e species
step 3, the olefin inserts to give the 16e alkyl tricarbonyl.
(Insertion) η2 to η1
step 4, Coordination of another equivalent of CO give
alkyl tetracarbonyl)
Step 5 Migratory insertion of CO gives the 16e .
Step 6, oxidative addition of hydrogen gives a
dihydrido complex, which
Step 7 releases aldehyde by reductive elimination
8 is unproductive and reversible
Ref: https://en.wikipedia.org/wiki/Hydroformylation#
The Catalytic Cycle For The Hydroformylation Of Alkenes By A
Cobalt Carbonyl Catalyst.

a) Production of terminal aldehyde b) Production of a branched aldehyde

Ref: Shriver et.al. (2014) Inorganic Chemistry, 6th edition

Cont’d

• Although the cobalt carbonyl catalyst allows the reaction to be useful, it

requires temperatures of approximately 1500C and a pressure of 200
atmospheres.
• Generally, the branched aldehydes are produced in greater quantity than straight
chain products.
• The linear aldehydes are converted to linear alcohols (found to be a big
handicap) that are used in the manufacture of detergents.
• The oxo process is also important for the production of precursors for making
polymers such as polyvinyl chloride.
 Cont’d

• When the linear aldehyde is required, such as for the synthesis of biodegradable
detergents, the isomerization can be suppressed by the addition of an alkylphosphine to
the reaction mixture.

• One plausible explanation is that the replacement of CO by a bulky ligand disfavours the
formation of complexes of sterically crowded 2-alkenes

Ref: Shriver et.al. (2014) Inorganic Chemistry, 6th edition

CHALLENGES

• Leads to formation of linear and branched isomers with the linear being more
valuable.
Challenge on the process
• Low product yield - linear product (80 %) and branched product (20 %)
• The active catalyst, [HCo(CO)4] is unstable, and its separation and recovery are
difficult
• The high partial pressure of CO (200 atm) and temperature of 1500C required for
the process means that plants are expensive to build and operate

• Few challenges faced the process was modified to use Rhodium-phosphine catalyst
 Study questions
• a) Predict the products formed when pent-1-ene reacts with CO and H2 in the presence of [Co2 (CO)8 ]. )
Comment on the effect of adding PMe3 or PPh3 to the reaction mixture.

• Answer: Answer By analogy with the cycles in Figs 25.7 and 25.8 we would expect two possible
intermediates to be formed following coordination of the alkene and hydrido migration

• Completion of the catalytic cycles will yield the linear and the branched products,
CH3CH2CH2CH2 CH2 CHO and CH3CH2CH2CH(CHO)CH3 respectively. The added phosphine would
coordinate to the catalysts and the increased steric crowding would inhibit production of the branched
product. This effect would be greater for PPh3 than for PMe3.
 Cont’d

• b) How would CO partial pressure affect the ratio of any linear and branched
products?
• Answer:
• Increasing the CO pressure would reduce the concentration of the coordinatively
unsaturated [Co(CO) 3 H] species. This species allows the coordinated alkene to
isomerize via β-hydride elimination. Thus, increasing the CO pressure will favour the
linear alkene.

Question:
Predict the product or products from the hydroformylation of cyclohexene
Hydroformylation Catalyst Using [Rh(CO)H(PPh3)3
Catalyst
• Loss of a phosphine ligand to form the coordinatively unsaturated 16-electron
complex
• Promotes the reaction at moderate temperature and 1ATM unlike Cobalt
• favors linear aldehyde products, it competes with the phosphine-modified
cobalt catalyst in industry.
• Question:
• Predict the influence of added triphenylphosphine on the rate of
hydroformylation catalysed by [Rh(CO)H(PPh3)3
Catalytic Cycle For The Phosphine Modified Rhodium-catalyzed
Hydroformylation

Sciencedirect.com
Schematic representation of the
hydroformylation catalytic
cycle with monophosphine
rhodium catalyst
REF Vladica Bocokić Thesis-
Research Gate
ADVANTAGE OF RHODIUM–PHOSPHINE CATALYSTS OVER
COBALT SYSTEMS

• Rhodium complexes are 100 to 1000 times more active than Co complexes, so much
less rhodium needs to be present in the reactor.
• The pressure (< 50 atm) and moderate temperature (100oC) required for reaction are
significantly lower than for the Co-based process, meaning that
• initial costs for plant construction is relatively low
• For linear aldehyde the rhodium-phosphine is the best despite the need to recover the
catalyst while cobalt catalyst is used for synthesis of medium- and long-chain
• The Rhodium catalyst are faster -Higher activity under milder conditions
• their feedstock utilization (or atom economy) is much better than that of cobalt catalysts
 Olefine Hydrogenation (Wilkinson’s Catalyst

• Wilkinson’s catalyst, [RhCl(PPh3)3],chlorotris-(triphenylphosphine)rhodium (I) and

related complexes are used for the hydrogenation of a wide variety of alkenes at pressures
of hydrogen close to 1 atm or less; suitable chiral ligands can lead to enantioselective
hydrogenations
• Wilknson catalyst is a homogeneous hydrogenation catalyst.
• It is square planar with Rh OS=+1
• .for a complex to function as a hydrogenation catalyst,
➢ it is necessary for it to be able to bond to hydrogen and to the alkene
➢the complex to be able to add hydrogen in an oxidative addition reaction, and that
process is characteristic of a metal in a low oxidation state
 Cont’d

• the hydrogen and alkene are part of the coordination sphere of the metal, a facile
means must be available for them to react. The overall reaction can be written as

H2 + alkene → alkane

RhCl(PPh3)3 meets the requirement. This complex is a coordinatively unsaturated

16-electron species that has become known s Wilkinson’s catalyst because it was
developed and utilized by the late Sir Geoffrey Wilkinson (who also received a Nobel
Prize in 1973 for work on the structure of ferrocene).
 Cont’d
• Metals which have d5 to d9 e.g. CuI, CuII, AgI, Hg(I), Ru(II). Ru(III), Co(I), Rh(I) etc. have been known
to activate hydrogen.
• The best known among these is [RhCl(PPh3)3]. - square planar
There are three ways in which molecular hydrogenation may be activated by hydrogen.
a) Oxidative addition of hydrogen to form an 18e
[RhCl (PPh3)3] + H2 → [Rh(H2)Cl(PPh3)2] – Unselective but [RhH(CO) (PPh3)3] only
Wilkinson’s catalys
for terminal alkenes (selective due to steric and electronic effects).The CO is in competition
with a -bonding Ligand in the trans position

(b) Heterolytic splitting: [RuIIICl6]3- + H2→ [RuIIIHCl5]3- + H+ + Cl-

(c) Homolytic splitting; 2[CoII (CN)5]3- + H2→ 2[CoIII H(CN)5]3-
• The oxidative addition reactions of a rhodium (I) compound showed that RhCl(PPh3)3 is an
effective homogeneous hydrogenation catalyst

• A study of its reaction kinetics indicates that the rate of hydrogenation is retarded by excess
triphenylphosphine indicating a pre-equilibria solvolysis.

L Cl L Cl L
Cl
-L,+S +H,-S
Rh Rh Rh
-H,+S
+L,-S
L L L S L H
S
L=PPh3
3 Steps Of Hydrogenation

The overall process involves

i. Oxidative addition of H2 to give an Oh complex

ii. Substitution by alkene of PPh3 in the trans position since it is labile (trans
effect) The alkene attaches to this intermediate.
iii. In order to form the reactive intermediate, a ligand must be lost and the large size
of the PPh3 ligand seems to be one factor that enhances its dissociation
iv. Reductive elimination of alkyl and hydride ligands to yield alkane
Cont’d

• The reaction scheme consists of a series of three steps

• hydrogen transfer to the alkene occurs.

• followed by another hydrogen transfer that occurs in conjunction with

reductive elimination of the alkane

• Regeneration of the catalyst.

Mechanism
PPh3
H Rh H
oxidative
addition Cl coordination
H H PPh3
R

PPh3
-PPh3 Cl
[RhCl(PPh3)2] RhCl(PPh3)3
+PPh3 H Rh H

R PPh3

reductive
elimination PPh3 migratory
Cl Rh H insertion
R
PPh3
H H
H
R
The catalytic cycle for the hydrogenation of terminal alkenes by Wilkinson’s
catalyst, https://edubuzznotes.com/hydrogenation-of-alkenes
 Application of Wilkinson’s Catalyst

• Hydrogenation of unsaturated hydrocarbons (olefins)can be employed for

• the hydro acylation of alkenes.
• The hydroboration and hydrosilylation of olefins
• Functionalized tri-substituted alkenes and internal alkynes can be subjected to
hydrogenation using Wilkinson’s catalyst in the presence of hydrogen and a strong base
where a highly reactive Rh(I) species having relatively superior catalytic activity is
formed
• The catalyst is highly effective in the selective hydrogenation of alkenes. It preferably
add H2 at the least hindered olefin when there are several olefins present.
 Isomerization of Alkenes
• Important for preparing specific isomers used as monomers in polymerization
• Involves change of bonding mode eg isomerization of 1-alkenes to produce 2-alkenes may
take place as the alkene changes from η2 to η3 in the transition state
• square planar complex of Rh1+ is one of the effective catalyst for the reaction
 Cont’d

• The process takes place in a series of steps:

1. substitution reaction in which the alkene replaces a ligand L followed by

2. the addition of H+and L to form a six-bonded complex.
3. A hydrogen transfer changes the alkene from η2 to η1 , which is reversed as the alkyl
group is converted into a 2-ene as a ligand L enters the coordination sphere of the
metal.
4. Reductive elimination by loss of L and H+ leads to a square planar complex in which
the alkene is present as the 2-ene.
5. Elimination of RCH=CH2CH3 as L enters the coordination sphere liberates the
product and reforms the catalyst.
Hydrosilylation using Rh catalyst

Ref Korbinian Riener et al 2012 (ACS Catal. 2012, 2, 4, 613–621)

 Polymerization Of Propylene Using An Organoaluminium – Titanium Catalyst
(Ziegler-nata Catalysts)

The Ziegler-Natta (ZN) catalyst, named after two chemists: Karl Ziegler and Giulio Natta;
Powerful catalyst with high linerlity and stereoselectivity
Ziegler–Natta catalysts that are employed are mainly of two broad categories and are clearly
distinguished based on their solubility.
• Heterogeneous supported catalyst. These are catalysts based on titanium compounds. Mainly
with organoaluminum compounds and cocatalysts during the polymerisation reactions.
• Apart from Ti, vanadium, chromium, and zirconium, as well as organic non-transition metal
derivatives can be used
 Cont’d

• Homogeneous catalysts. From the complexes of Hf, Ti,or Zr.

• used in combination with a different organoaluminum cocatalyst e.g
(methylalumoxane, MAO)
• They usually contain metallocenes but also feature nitrogen-based and multidentate
oxygen-based ligands.

• catalyst formed from group (3) metal alkyls (usually Et3Al or Et2AlCl) and some
transition metal (TM) compounds of group IV

[AlEt3] 3+ + TiCl3 → Et2AlCl + EtTiCl3

Reactions
1. Initiation step: activation of catalyst precursor: alkylation of TM cpd with soluble
Grp 3 metal alkyl to give catalytically active TM alkyl (Formation of alkene-metal
complex)
2. Propagation step: migration of olefin or chain growth where the process starts over
nd over, giving linear polymer
3. Termination step or β-elimination: Chain transfer& catalyst decomposition. Final
step of the chain growing polymer, it gives the desired polymer
4. Note: The catalyst is sensitive to O2, moisture and other heteroatoms containing
impurities.
5. polymerization occurs at a solid surface (a heterogeneous catalyst)
 1. STEP 1: Initiation Step:)
Alkylation Of TM Cpd With Soluble Grp 3 Metal Alkyl to give Catalytically
Active TM Alkyl (Formation 0f Alkene-metal Complex
STEP 2: Propagation Or Migration Of The Alky Gp Olefine
• The olefin binds to the metal thr’ double bond which donates e to empty d oorbital
• Migration of alkyl group to olefin as shown below
• Formation of alky metal bond that is forming the polymer.
Termination Or  Elimination

• To stop the polymerization, we may interrupt the process by  elimination of a metal

hydride or by hydrolysis as follows.
 APPLICATIONS

• The Ziegler-Natta catalyst polymerisation is a beneficial and versatile reaction for producing
polymers. Some of the most popular applications of this catalyst are;
• They are used for the production of High (HDPE), linear low-Density Polyethylene.(LLDPE) and
ultra-high molecular weight polyethylene (UHMWPE)
• HDPE- Used in garbage containers, water pipes, detergent bottles
• LLDPE- Cables coverings – due short brances,tough, flexible and stress-cracking resistance.
• UHMWPE: (Mw 3.5M)-extremely tough &chemically resistant- gears and artificial joints
• Roduction of thermoplastic polyolefins, polybutylene, crystalline polypropylene and carbon nano
tubes nanocomposites.
• Commercially viable and production of jpbs where quality of peoples lifes is improvedWidely used
in clothing, medical plastics, food packing and building construction
 The Wacker Process or Smidt Reaction -Conversion of
an Alkene to an Acetaldehyde

• Used to produce ethanal from ethene and oxygen using palladium catalyst to
oxidize the alkene, with the palladium being re-oxidized via a secondary copper
catalyst

• Oxidation of ethylene into acetaldehyde – important industrial process

• Acetaldehyde, vinyl acetate and vinyl chloride are important industrial intermediates for
the manufacture of many compounds
.
Cont’d

a) Acetaldehyde may be produced by bubbling ethylene into aqueous

solution of a soluble Pd (II) salt in the presence of O2.
(b) If the reactions are carried out in presence of acetate, vinyl acetate is
produced
(c) Vinyl Chloride is among the products formed when ethylene is
passed into a suspension of PdCl2 in a non-aqueous solvent
 MAIN REACTIONS

i) CH2=CH2 +1/2O2 (PdCl4/H2O, • Product formation

CUCl2) → CH3CHO C2H4 + PdCl4 +H2O → CH3CHO +Pd0 +2HCl + 2Cl
• Catalyst regeneration
Acetaldehyde Pd(o) + 2CuCl2 + 2Cl-→PdCl42- + 2CuCl
ii) CH2=CH2 + PdCl2 → Co-Catalyst regeneration
CH2=CHOAC + Pd + H+ +2Cl-
4CuCl + 4H3O+ + 4Cl- + O2 →4CuCl2 + 6H2O.
vinyl acetate
NOTE
All the catalysts are regenerated and only the alkene and oxygen
iii) CH2=CH2 + PdCl2 + 2L →
are consumed.
CH2=CHCl + [HPdClL2]
Also you will notice that without CuCl2 and HCl as oxidising
Vinyl chloride agent, the Pd would precipitate out and the reaction would stop
 Mechanism

• Kinetic studies in aqueous solution suggest the following rate low

d[CH3CHO] = K[C2H4][PdCl4]
dt [H+][Cl-]2
• Whereas there is a 1st order dependence on ethylene and the Palladium halide,
an inverse dependence on [H+] and an inverse square dependence on [Cl-]
exist.
• Use of D2O proves that the H2 does not come from the solvent but from the
olefine
 MECHANISM -USE OF D2O (DEUTERIUM OXIDE) SHOWS
THAT H COMES FROM OLEFIN AND NOT SOLVENT

a) Olefin insertion which substitute a Cl- • b) Substitution of another Cl- by H2O account
ion for the inverse square dependence on Cl-
concentration.

-
Cl Cl Cl OH2

Pd CH2 + Cl-
Pd + H2O
CH2 Cl CH2
Cl
CH2
 Mechanism Cont’d

C) Loss of H+ to form a hydroxo-metal d) The rate determining step is the migration

complex of the hydroxyl ligand to the co-ordinated
olefin.

2-
Cl Cl Cl OH 2-
Cl Cl Cl S
Pd CH + H3O+
+ +H2O 2
Pd Pd + H3O+
Cl Pd CH2 + +H2O
CH2 CH2CH2OH
Cl Cl
OH2
OH2 CH2
 2-
Cl Cl Cl S

Pd + H3O+
Pd CH2 + +H2O
CH2CH2OH
Cl
OH2 CH2
 The next step is thought to be β-elimination of the H2 to give the product. The most
important feature for Pd chemistry is the high affinity of the metal for hydrogen.

S Cl H
Cl
Pd Pd
Cl CH2
CH2CH2OH Cl
C H
H O

Finally, acetaldehyde is produced in another β-elimination followed by a

base dissociation reaction
Production of Aldehyde and Catalyst
J. Tsuji, "Palladium Reagents and Catalysts", First Edition 2004,
Wiley, 29-35.
 QUESTIONS

1. In the Wacker process, where does the hydrogen in the product come from?

2. How is CuCl2 (co-catalyst) regenerated from CuCl in Wacker process?

3. In Ziegler-Natta catalyst, why is Et3Al and titanium chloride or Zirconium chloride

respectively preferred instead of Et2AlCl?

4. Draw the catalytic cycle for hydrogenation using Wilkinson'$ catalyst Label the
mechanism at each of the steps the catalytic cycle_ Hz RhCI(PPh;)
 Monsanto Process
• The Monsanto process is an industrial method for the manufacture of acetic acid by catalytic
carbonylation of methanol
• The reaction involves catalysis with HI and [RhI2(CO)2]- as a co-catalysts
• developed in 1970s by the Monsato German chemical company, to replace the BASSF process (Co
catalyst)
• operates at a pressure of 30–60 atm and a temperature of 150–200 °C and gives a selectivity greater than
99%to acetic acid
• The Monsanto process has largely been replaced by the Cativa process; a similar iridium-based process
developed in 1966 by Bp Shell chemicals
• BASF process was improved by the Monsanto Company in 1966
• rhodium is 103 to 104 times more active than the corresponding cobalt catalyst, which means that much
lower CO pressures and moderately lower temperatures are required
• 1. Jane Hjones platinum metal Rev, 2000, 44, (3) 94
• 2. Hosea Cheungetal "Acetic Acid in Ullmann's Encyclopedia of Industrial Chemistry, 2002,Wiley-VCH Weinheim.
doi:10.1002/14356007.a01_045
Comparison of Co and Rh Catalysts

• Parameters Cobalt Rhodium

• Concentration ~ 10-1 M ~ 10-3 M
• Temperature ~ 230° C ~180° C
• Pressure 500-700 atm 30-40 atm
• Selectivity 90% > 99%
• H2 effect CH4, CH3CHO, EtOHbyproducts no adverse effect
• The catalytically active species is the anion cis-[Rh(CO)2I2]−
• Invoves the insertion of carbon monoxide (CO) in methanol in presence of a catalyst (carbonylation
of methanol)
• Overall reaction:

MeOH + CO (HI/RHI2(CO)2) 1800C, 30-40ATM → CH3COOH

The role of iodide is simply to promote the conversion of methanol to methyl iodide, the species which
then undergoes reaction with the Rh metal catalyst:
MeOH + HI → MeI + H2O
Highly selective, gives high yield,
About 1,000,000 tons of acetic acid are produced every year using this process

Ref Adv. Organomet. Chem. 1979, 17, 255

 The process
1. Production of cis [Rh (CO)2I2]
2. Production of methyl iodide from methanol
MeOH + HI → MeI + H2O
3. Oxidative addition of methyl iodide to cis [Rh (CO)2I2] to
form [(CH3)Rh(CO)2I3]−
4. Migration of a methyl group to the adjacent CO group to
give [(CH3CO)Rh(CO)I3]−.
5. Insertion of CO group to give an intermediate grp (18
electron)
6. Reductive elimination to release acetyl iodide (CH3C(O)I).
7. Hydrolysis of acetyl iodide to give acetic acid and hydrogen
iodide
Cont’d
The reaction is a first-order with respect to methyl iodide and [Rh(CO)2I2]−
• Hence the oxidative addition of methyl iodide to the RH-catalyst is proposed as
the rate - determining step
• The alkyl species, [Rh(CO)2(Me)I3]- is very reactive in the CO insertion step,
• When the water content is less than 8 wt%, the rate determining step becomes the
reductive elimination of the acyl species, from catalyst species
(RhI2(CO)2COCH3).
• high amounts of H2O is needed but this increases the amount of the highly
corrosive HI present leading to engineering problems
Cont’d
Roland Mattern - Roland1952 Wikipendia
LIMITATIONS

There are two major concerns:

1.Rhodium is an expensive starting material. 1 mole of RhCl3.3H2O costs ~
$30,000
2.I2 is cheap (about $20 per mole) but is extremely corrosive. Other halogens or
halogen substitutes do not work nearly as well. This make the whole process
expensive
 The CATIVA Process For The Manufacture Of Acetic Acid
• Introduced in 1996 where carbonylation of methanol to acetic acid was announced by BP
Chemicals
• Iridium (ir) –Cativa, catalyst replaced Rh catalyst
• it offer significant improved method to the monsanto one
• A lot of saving (Cheap) on capital required to build the plant (rhodium ($5200 per troy oz)
and iridium ($300 per troy oz)
• Batch testing I 1990
• Commercial production in 1995
• Has a substantial advantage than Monsanto
• .
 Cont’d

• The anionic iridium cycle, is similar to the rhodium cycle, but contains sufficient key
differences to produce the major advantages seen with the iridium process

• Studies have shown that the oxidative addition of methyl iodide to the iridium centre is
about 150 times faster than the equivalent reaction with rhodium

• The slowest step in the cycle is the subsequent migratory insertion of CO to form the
iridium-acyl species
Cont’d

• Rate is proportional to [catalyst] X [CO]/ [I-], therefore

• Inverse dependent to iodide Concn suggests that very high reaction rates should
be achievable by operating at low iodide concentrations

• Removal of iodine promote the rate

• Promoter: simple iodide complexes of zinc, cadmium, mercury, gallium and
indium & Carbonyl-
• iodide complexes of tungsten, rhenium, ruthenium and osmium.
 Cont’d
Compare the two processes

CATIVA Process: Catalytic cycle for the

Monsanto-Rh catalyzed carbonylation
carbonylation of methanol using iridium
http://www.ilpi.com › organomet › monsanto
Ref: Jane H. Jones (2000), Platinum Metals Rev., 44, (3), 94
Cativa™ Iridium-based System Delivers Many Benefits Over The
Conventional Monsanto Rhodium-based Methanol Carbonylation Process
These benefits include: •
• an inherently stable catalyst system
• less dependence on CO partial pressure

• the reactor can run with a lower vent rate, which results in a higher utilisation of CO,
which can be further improved by the addition of selected promoters. These effectively
remove the dependence of reaction rate on the CO partial pressure.

• plants can operate with a higher reactor productivity, and higher rates still have been
demonstrated at pilot plant scale
•
Cont’d
• the production of by-product propionic acid is reduced, leading to reduced purification
costs

• the level of acetaldehyde in the Cativa™ process is lower than in the rhodium process,
giving a fundamentally purer product. Hydrogenation of any unsaturated species present is
catalysed by the iridium species, resulting in almost complete elimination of unsaturated
condensation products and iodide derivatives.

• Thus, the reduced environmental impact of the Cativa™ system along with the cost
reductions have allowed substantial benefits to be gained from this new industrial process
for the production of acetic acid.
 Cont’d

The main differences between the Ir and Rh catalyst systems:

• Migratory insertion of the Ir-CH3 and Ir-CO ligands. Is the rate determining step for
Ir

• The MeI oxidative addition step is faster for Ir due to its lower electronegativity.

• Since Ir-ligand bonds is stronger, it slow down the migratory insertion step and
reductive elimination steps

• Unlike in Rh catalyst, only fewer side reactions in the Ir system which make M(III)
complexes inactive
Study questions
1. In the Wacker process, where does the hydrogen in the product come from?

2. How is CuCl2 (co-catalyst) regenerated from CuCl in Wacker process?

3. Draw the catalytic cycle for the Ziegler–Natta polymerization of

propene. Explain each of the steps involved and predict the physical
properties of the polymer produced

4. In Ziegler-Natta catalyst, why is Et3Al and titanium chloride or Zirconium

chloride respectively preferred instead of Et2AlCl?
• Silicones are polymeric organosilicon compounds containing Si-O-Si linkages with a
general formula (R2SIO).
• Prepared mainly by the hydrolysis of alkyl or aryl substituted silicon halides and
subsequent condensation (Loss of water). Three classes are:
❖1. Linear
❖2. crosslinked
❖3. cyclic
❖The chlorosilane is prepared by
❖SiCl4 + 2 CH3MgCl → (CH3)2SiCl2 + 2MgCl2
❖CH3)2SiCl2 + H2O → (CH3)2Si(OH)2 + 2HCl
Linear
Linear
Cross Linked
Cyclic
Other Examples Of Crosslinked
PROPERTIES

• Cross linked depend on the alkyl group

• Range from oily for the lower silicones to rubber like solids for higher silicones

• Water repellant (presence of organic group)

• Low Thermal conductivity and electrical insulators

• Chemically inert
 Properties cont’d

• Has high resistance to oxygen, ozone, and ultraviolet (UV) light.

• Very Low toxicity

• Viscosity of the silicon oil remains constant and does not change with temperature
and is not affected cold weather (winter)

• High gas permeability and high thermal stability

USES

• Silicones are used for low temperature lubrication and in vacuum pumps, high
temperature oil baths etc

• They are used for making water proofing clothes

• They are used as insulting material in electrical motor and other appliances

• They are mixed with paints and enamels to make them resistant towards
high temperature, sunlight, dampness and chemicals.
•
Cont’d

• Used in computer and engineered spacecraft,

• Used in renewable energy eg turbines and solar energy

• Widely used in personal care product, shampoos etc

• Lubricants: silicone grease

• Sporting apparels and toys