Catalysis

The catalysis of organic reactions1 is one of the most important applications of organometallic
chemistry and has been a significant factor in the rapid development of the field as a whole.
Organometallic catalysts now have numerous applications in the pharmaceutical,2 fine chemical, Page | 1
and commodity chemical industries and are beginning to contribute to the rising topics of energy
and green chemistry. By bringing about a reaction at lower temperature, a catalyst can save
energy input and, by improving selectivity, can minimize product separation problems and waste
formation.

There are two types of catalyst one is homogeneous catalysts, another is or heterogeneous
catalysts, so named because the catalyst and substrates are in the same phase
only in the first case. In second one the substrate and catalyst are in different phase. Each type
has its advantages and disadvantages. Homogeneous catalyst must be separated from the product
( a negative feature) but operate in low temperature and pressure and usually good selectivity
(all these are positive features) Where as in heterogeneous catalyst can easily be separated from
the reaction product ( a very positive feature) but require high temperature and pressure and
lead to mixture of products i.e.; have very low selectivity.

(a) (b)

Figure – a) A catalyst lowers the activation energy for a chemical reaction. Here, the
uncatalyzed conversion of substrate S to product P passes by way of the high-energy transition
state TS. In this case, the metal-catalyzed version goes via a different transition state TS′, which
is very unstable in the free state but becomes viable on binding to the catalyst as M.TS′. The
arrow represents the M–TS′ binding energy. (b) Typical catalytic cycle in schematic form.

A catalytic cycle consists of a set of reactions that occurs only in the presence of a catalyst and
that leads to product formation from reactants, or substrates. The catalyst can mediate an
indefinite series of cycles and is thus only needed in substoichiometric amount relative to
reactants or products. The catalyst loading is typically from 1 ppm to 1% relative to reactants,
meaning that the number of cycles initiated by each molecule of catalyst runs from 106 to 102,
respectively. Catalysis can be useful either by speeding up a reaction or modifying its selectivity,
or both.

Here in we discussed the following process. Page | 2

1. Hydrogenation of alkene:
Although the reaction of hydrogen gas with ethylene is thermodynamically favourable it
does not takes place at room temp. and pressure. However, presence of metallic Ni, Cu,
Pd or Pt, the reaction is fast and complete.
H2C=CH2 + H2 → H3C-CH3 ( ∆ H0 = -136 kj/mol and ∆ G0 = -101 kj/mol)
Most important catalyst for Hydrogenation is Wilkinson catalysts, (a homogeneous
catalysis) add H2 to an unsaturated C=X bond (X = C, N, O). Substrates range from
alkenes and alkynes to the more challenging cases of arenes, nitriles, and esters.
Wilkinson’s catalyst, RhCl(PPh3)3 , a square planar , 16 electron Rh(I) complex.

(Wilkinson’s catalyst )

Hydrogen addition to give a dihydride leads to labilization of one of the PPh3 ligands to give a
site at which the alkene binds. The alkene inserts into the Rh–H bond, as in isomerization, but
the intermediate alkyl is irreversibly trapped by RE with the second hydride to give an alkane.
The mechanism for the hydrogenation of alkenes by Wilkinson’s catalyst (L = PPh3).
involving prior dissociation of PPh3 before H2 binding in which L′ = solvent.
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Fig. Catalytic cycle of Wilkinson Catalyst for hydrogenation af alkene

2. Hydroformylation reaction ( Oxo process):

Hydroformylation, also known as oxo synthesis or oxo process, is an industrial process for the
production of aldehyde from alkenes. with carbon monoxide and hydrogen. The name
Hydroformylation arises because of the net addition of a formyl group (-CHO) and
a hydrogen atom across a carbon-carbon double bond. Hydroformylation of propelene
Hydroformylation of propylene yielding n-butanal and iso-butanal is one of the most important
industrial processesand become one of the most important large-scale industrial processes
(approximately 75% of the world consumption) to generate oxo-compounds (aldehydes,
alcohols, and carboxylic acids), effectively driven by homogeneous catalyst Co2(CO)8.It was
discovered by Roelen in 1938, and is the oldest and largest volume catalytic reactions of alkene
to aldehyde.

RCH=CH2 +2CO +H2 → RCH2CH2CHO + RCH2(CHO)CH3 [Co2(CO)8 acts as catalyst]

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Figure: Isomerization and hydroformylation of the indicated alkenes by HCo(CO)4. The

position and % abundance of the resulting formyl group is shown.

The active catalyst, HCo(CO)4, formed by the reaction of Co2(CO)8 and H2 remain equilibrium
with dicobalt octacarbonyl, Co2(CO)8. The mechanism of the cobalt-catalyzed hydroformylation
reaction has been studied extensively, and the currently accepted mechanism is illustrated in
below. Each step in the mechanism is reversible, with the final product forming step being the
least likely to backtrack.

in order for alkene or H2 to coordinate to the cobalt catalyst a CO

Figure: Mechanism for hydroformylation by HCo(CO)4 showing production of linear and

branched aldehyde products. Reaction steps are in equilibrium, but single direction reaction
arrows are shown for simplicity.
In order for alkene or H2 to coordinate to the cobalt catalyst a CO must dissociate. HCo(CO)4 is
an 18 electron-saturated species and cannot coordinate an alkene until one of the coordinated CO
ligands dissociates. The rate of hydroformylation increases with increasing hydrogen and alkene
concentrations, but decreases with increasing carbon monoxide partial pressures. This suggests
that rates of hydroformylation would be satisfactory at high H2 and low CO partial pressures. Page | 5
Unfortunately, HCo(CO)4 decomposes to cobalt metal at operational temperatures unless
sufficient CO pressure is present. The pressure of CO needed to stabilize the HCo(CO)4 catalyst
increases exponentially with temperature. Therefore, high pressures of both H2 and CO are
required in order to stabilize theHCo(CO)4 catalyst at the temperatures necessary for practical
industrial rates. The HCo(CO)4 catalyst requires high pressures of H2/CO (∼300 bar) and
temperature ~180˚ C.

Phosphine-Modified Cobalt Process:

Shell Chemical developed the phosphine-modified cobalt technology in the early 1960s (4,5).
Adding an electron-donating phosphine ligand to the cobalt made it more electron-rich, which, in
turn, allowed the CO ligands to bind more strongly to the cobalt center via π-backbonding.

This has four significant effects:

1. The HCo(CO)3(PR3) catalyst is now far more resistant to loss of CO and hydrogen, which
inhibits decomposition of the catalyst to cobalt metal. This enables the use of lower CO pressures
at higher temperatures, which results in lower overall H2/CO process pressures: ∼70 vs 300 bar
for HCo(CO)4; ∼190 vs. 180°C for HCo(CO)4.

2. The stronger CO bonding makes CO dissociation more difficult and lowers the activity of the
HCo(CO)3(PR3) catalyst significantly relative to HCo(CO)4.

3. The phosphine ligand increases the sterics around the cobalt atom and more strongly favors
the reaction of the cobalt hydride with alkene to make a linear alkyl intermediate that goes on to
form a linear aldehyde. This produces a much higher L:B aldehyde ratio relative to HCo(CO)4.

4. The electron-donating phosphine ligand makes the cobalt-hydride more “hydridic.” This
makes the HCo(CO)3(PR3) catalyst a much better hydrogenation catalyst relative to HCo(CO)4.
The Shell HCo(CO)3(PR3) catalyst is active under hydroformylation conditions for
hydrogenating the aldehyde to the desired alcohol product. Unfortunately, HCo(CO)3(PR3) can
also hydrogenate alkenes to alkanes, which is a very unwanted side reaction.
 Page | 6

Figure: Mechanism for hydroformylation by HCo(CO)3(PR3) showing production of linear

aldehyde product and the subsequent hydrogenation to make alcohol. Reaction steps are in
equilibrium, but single direction reaction arrows are shown for simplicity.

Oxo Product Uses:

n-Propanol and n-propyl acetate account for about 70% of the U.S. propionaldehyde derivative
market (see also PROPYL ALCOHOLS). These compounds are used
principally in flexographic and gravure inks, which require volatile solvents to
prevent smearing and ink accumulation on the printing presses (see also PRINTING
PROCESSES). Some propanol is also converted into n-propylamines that are important pesticide
intermediates (see also PESTICIDES). n-Propanol is also employed as a
precursor for glycol ethers having primary usage in surface coatings applications
and flexographic printing inks (see also GLYCOLS). The other propionaldehyde
derivative, propionic acid, is used principally in grain and feed preservative
applications (see also FEEDSAND FEED ADDITIVES). Sodium and calcium propionates
are used in both food and animal feed applications (see also FOOD ADDITIVES). Some
propionic acid is converted into herbicides, such as 3,4-dichloropropionanilide, and
into cellulose acetate propionate, a plastic sheeting and molding precursor.
The highest volume oxo chemical in the United States, n-butyraldehyde, is
converted mainly into n-butanol, employed chiefly to produce butyl acrylate and methacrylate
(see also ACRYLICACIDAND DERIVATIVES), followed by 2-ethylhexanol
(2EH). In contrast, the principal n-butyraldehyde derivative in Europe and Japan
is 2-ethylhexanol, the precursor to the poly(vinyl chloride) (PVC) plasticizer, DOP.
1,4-Butanediol (BDO) goes primarily into tetrahydrofuran (THF) for production of
polytetramethylene ether glycol (PTMEG), used in the manufacture of
polyurethane fibers, for example, Spandex. THF is also used as a solvent for PVC
and in the production of pharmaceuticals. Lesser amounts of BDO are employed in
the production of polybutylene terephthalate resins and γ-butyrolactone.
The principal C5 valeraldehyde derivatives, n-amyl and 2-methylbutyl alcohols, are used
predominantly to make zinc diamyldithiophosphate lube oil additives (see also AMYL
ALCOHOLS; LUBRICATIONAND LUBRICANTS), which are employed Page | 7
primarily in automotive antiwear applications. Similarly, the n-valerate and 2-
methylbutyrate esters of pentaerythritol and trimethylolpropane are used in
aeromotive synlube formulations and as refrigerant lubricants.
C7–C9 oxo-derived acids are the principal derivatives of the C7–C9 oxo
aldehydes, and in analogy to C5 oxo aldehyde market applications are chiefly
used to make neopolyol esters, that is, those based on neopentyl glycol, trimethylolpropane, or
pentaerythritol. These synlubes are employed almost entirely in
aeromotive applications. Heptanoic acid is also employed to make tetraethylene
glycol diheptanoate, a plasticizer used with poly(vinyl butyral).
Several alcohols in the C6–C13 range are produced by oxo reactions and are
used in both plasticizer and detergent applications. Linear C12–C15 alcohols
are employed primarily in detergent applications. Slightly more than 50% of
the ∼620,000 metric tons of domestic U.S. detergent alcohol capacity is produced
by hydroformylation of linear olefins from n-paraffins or ethylene chain-growth
products (eg, SHOP). The remainder is produced from natural sources. Detergent
alcohols are converted principally into alcohol sulfates, ethoxylates, alcohol ether
sulfates, and fatty amines. Only a small (∼1%) fraction of the detergent alcohols
are destined for direct consumption

3. Wacker Process:
This process involve a catalytic oxidation of alkene to form an aldehyde in presence of
[PdCl4]2- as a catalyst.
H2C=CH2 +1/2 O2 → CH3CHO [[PdCl4]2- as a catalyst]

It’s one of the examples of the successful industrial application of homogeneous catalysis. In the
reaction Pd2+ is reduced to palladium metal, which is reoxidized by Cu2+. The reduced Cu+ is
oxidized back by oxygen to Cu2+. The overall mechanism for this reaction is outlined below.

Scheme-1
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Scheme-2: Catalytic loop of Wacker process

The catalytic features of the Wacker process are given below.

 The first step in this the formation of the olefin complex [Cl3Pd(C2H4)]-.
 The metal activated olefin is susceptible to nucleophilic attack by water. This generates
the complex [Cl3Pd-CH2-CH2-OH]2-.
 β-hydrogen transfer leads to the second olefin complex
 The next step not understood properly, leads to the alkyl complex, where the alkyl
complex has a hydroxyl substituent.
 This undergoes reductive elimination to afford the aldehyde, and Pd(0). Note that if there
was no way of catalytically reoxidizing the Pd(0), the reaction will be dead now.
Fortunately, Cu2+ is a good catalyst, which can oxidize Pd(0) to Pd2+. The Cu+ thus
generated is reoxidized by oxygen in another catalytic cycle. In this way the expensive
palladium reagent is reutilized
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Scheme 2a: Analytic cycle of the Wacker process (Angew. Chem. Int. Ed. 2009, 48, 9038 –
9049)

4. Synthetic Gasoline

Fischer−Tropsch synthesis is a catalyzed chemical reaction in which synthesis gas (syngas), a

mixture of carbon monoxide (CO) and hydrogen (H2), is converted into gaseous, liquid, and solid
hydrocarbons and related oxygenated compound under high pressure (>25 bar) and moderate
temperature (~300°C) in the presence of a catalyst group VIII metals. Fe or Co in Alumina.

nCO + (2n+1)H2 → CnH2n+2 + nH2O

A Fischer−Tropsch plant incorporates three major process blocks: (1) production of synthesis
gas, i.e. a mixture of carbon monoxide and hydrogen (steam reforming), (2) conversion of
synthesis gas to aliphatic hydrocarbons and water (Fischer−Tropsch synthesis process), and (3)
hydrocracking of the longer chain, waxy synthetic hydrocarbons to fuel grade fractions. Of these
three steps, the production of synthesis gas is the most energy intensive as well as expensive and
this step can account for as much as 50 to 75% of capital costs. While extensive research has
been undertaken with the aim of finding process improvements in all three steps, this step has
received the greatest attention. In great measure, this has significantly impacted on allowing
plants the ability to attain a scale almost inconceivable until recent times. The technological
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advances relating to this step are thus discussed in addition to the actual Fischer−Tropsch
synthesis process. In summary, the Fischer−Tropsch process yields a wide range of
hydrocarbons, from low-boiling gases to high-boiling wax.

5. Alkene polymerization:
Alkene polymerization is one of the most important catalytic reactions in commercial use and
was an important advance in polymer and materials science. The Ziegler–natta catalyst
(TiCl3/Et2AlCl), for which they won the nobel Prize in 1963, account for more than 50 million
tons of polyethylene and polypropylene annually. In contrast with the 200°C and 1000 atm
conditions required for thermal polymerization, Ziegler–natta catalyst is active at 25°C and 1
atm. not only are the conditions milder, but the product also shows much less branching. This led
to the commercialization of linear low-density polyethylene (LLDPE). Propylene, which does
not form useful polymers thermally, now gives highly crystalline stereoregular polymer ( given
below)

Polymers are large molecules with molecular weights in the range of 104 to 106. These
consist of small building units known as monomers. For example polyethylene is made
up of ethylene monomers. Poly vinylchloride is built from vinyl chloride and similarly
polystyrene is made from styrene. In all of these cases a single monomer is repeated
several times in the polymer chain. The number of repeating units determines the
molecular weight of the polymer.
There are typically three parts to most polymerization reactions: i) Initiation, ( ii) Propagation and( iii)
Termination.
Mechanism : The first step is the alkylation of the titanium center. Please note that since this is a
heterogeneous catalyst we are looking at the surface of the catalyst. Obviously this implies
coordination unsaturation at titanium . In the bulk sample the titanium has a coordination number
of six. However, at the surface the coordination of titanium is incomplete. This site can be taken
up by a ligand such as olefin. Subsequent steps are the olefin insertion and the creation of a long
alkyl chain. The chain terminates by elimination.
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References:

1. Inorganic Chemistry: Principals of structure and reactivity, J. E. Huheey, E.A. Keiter,

R. L. Keiter, Addison –Wesley publishing Company, 4th Edition.
2. The Organometallic Chemistry of the Transition Metals, Robert H. Crabtree, John
Wiley & Sons, Inc.6th Edition.
3. John A. Keith and Patrick M. Henry, Angew. Chem. Int. Ed. 2009, 48, 9038 – 9049.
4. Hydroformylation (oxo) catalysis, George G. Stanley, John Wiley & Sons, Inc, DOI:
10.1002/0471238961.1524150209121.a01.pub2.