CATALYSIS

Reactions involved in catalytic process

involving organometallic complexes
Dissociative ligand substitution reaction
Oxidative addition & Reductive elimination

Oxidation number & coordination number increases by 2

Example of OA
Question
β-elimination in organic compounds
β-elimination in organometallic complexes
What is Wilkinson’s Catalyst?
• [IUPAC Name: chloridotris(triphenylphosphine)rhodium(I)]
• It is a coordination compound whose coordination centre is rhodium.
• It is extensively used as a catalyst in the hydrogenation of alkenes.
• Chemical formula: [RhCl(PPh3)3] where ‘Ph’ denotes a phenyl group. At
ambient temperatures, this coordination complex exists as a reddish-brown
solid.
• The structure adopted by Wilkinson’s Catalyst is square planar (slightly
distorted). The rhodium centre is bound to four ligands in this compound.
• Wilkinson’s catalyst is named after the English chemist Sir Geoffrey
Wilkinson. I
Physical Properties

• The molar mass of Wilkinson’s catalyst is 925.22 grams/mole

• It’s melting point ranges from 518 to 523K
• It is insoluble in water. However, it is soluble in many hydrocarbon-
based solvents such as benzene and tetrahydrofuran
Chemical Properties

• Wilkinson’s catalyst has a square planar coordination geometry

• It reacts with carbon monoxide to yield [RhCl(CO)(PPh3)2]
• This coordination compound undergoes dimerization when stirred into
a solution of benzene. The chemical composition of the dimer can be
expressed as [RhCl(PPh3)2]2
 Preparation of Wilkinson’s Catalyst

• Wilkinson’s catalyst can be prepared by reacting hydrated rhodium(III) chloride with excess
triphenylphosphine in the presence of ethanol (which acts as a refluxing agent).
• Here, the triphenylphosphine (denoted by the chemical formula P(C6H5)3) acts as a reducing
agent which has the ability to oxidize itself from an oxidation state of +3 to an oxidation
state of +5.
• During the synthesis of Wilkinson’s catalyst, one equivalent of triphenylphosphine reduces
rhodium(III) to rhodium(I) while three other equivalents bind themselves to the metal as
ligands in the final product.

4P(C6H5)3 + RhCl3(H2O)3 → RhCl(P(C6H5)3)3 + OP(C6H5)3 + 2HCl + 2H2O

 Mechanism of Catalysis for the Hydrogenation of
Alkenes
• Initially, a 14-electron or 12-electron complex is formed from the
dissociation of 1 or 2 triphenylphosphine ligands.
• Now, the oxidative addition of molecular hydrogen (H2) to the metal core of
Wilkinson’s catalyst (rhodium) occurs.
• The third step of the mechanism involves the formation of a pi complex
with the alkene.
• The hydrogen is inserted into the complex via migratory insertion which
could proceed through intramolecular hydride transfer or through olefin
insertion.
• Finally, reductive elimination occurs at the pi complex to regenerate the
catalyst and afford the required alkene product.
Fischer Tropsch Process

• The Fischer–Tropsch process is a collection of chemical

reactions that converts a mixture of carbon monoxide and
hydrogen into liquid hydrocarbons.
• These reactions occur in the presence of metal catalysts,
typically at temperatures of 150–300 °C (302–572 °F) and
pressures of 1 to 10 atmosphere.
• The process was first developed by Franz Fischer and Hans
Tropsch in the year 1925.
• The Fischer–Tropsch process is an important reaction in both coal
liquefaction and gas to liquids technology for producing liquid
hydrocarbons.
• In the usual implementation, carbon monoxide and hydrogen, the
feedstocks for FT, are produced from coal, natural gas, or biomass in a
process known as gasification.
• The Fischer–Tropsch process then converts these gases into a synthetic
lubrication oil and synthetic fuel.
• The Fischer–Tropsch process has received attention as a source of
low-sulphur diesel fuel and to address the supply or cost of petroleum-
derived hydrocarbons.
 Fischer–Tropsch intermediates and elemental
reactions
• Converting a mixture of H2 and CO into aliphatic products is a multi-step reaction
with several intermediate compounds.
• The growth of the hydrocarbon chain may be visualized as involving a repeated
sequence in which hydrogen atoms are added to carbon and oxygen, the C–O bond
is split and a new C–C bond is formed.
• For one –CH2– group produced by CO + 2 H2 → (CH2) + H2O, several
reactions are necessary:
•  Associative adsorption of CO
•  Splitting of the C–O bond
•  Dissociative adsorption of 2 H2
•  Transfer of 2 H to the oxygen to yield H2O
•  Desorption of H2O
•  Transfer of 2 H to the carbon to yield CH2
• The conversion of CO to alkanes involves hydrogenation of CO, the hydrogenolysis
(cleavage with H2) of C–O bonds, and the formation of C–C bonds. Such reactions are
assumed to proceed via initial formation of surface-bound metal carbonyls.
• The CO ligand is speculated to undergo dissociation, possibly into oxide and carbide
ligands. Other potential intermediates are various C1 fragments including formyl (CHO),
hydroxycarbene (HCOH), hydroxymethyl (CH2OH), methyl (CH3), methylene (CH2),
methylidyne (CH), and hydroxymethylidyne (COH). Furthermore, and critical to the
production of liquid fuels, are reactions that form C–C bonds, such as migratory insertion.
• Many related stoichiometric reactions have been simulated on discrete metal clusters, but
homogeneous Fischer–Tropsch catalysts are poorly developed and of no commercial
importance.
• Addition of isotopically labelled alcohol to the feed stream results in incorporation of
alcohols into product. This observation establishes the facility of C–O bond scission.
• Using 14C-labelled ethylene and propene over cobalt catalysts results in incorporation of
these olefins into the growing chain. Chain growth reaction thus appears to involve both
‘olefin insertion’ as well as ‘CO-insertion’
Ziegler Natta Catalyst: Alkene polymerization
• An efficient and stereospecific catalytic polymerization procedure was developed
by Karl Ziegler (Germany) and Giulio Natta (Italy) in the 1950’s.
• Their findings permitted, for the first time, the synthesis of unbranched, high
molecular weight polyethylene (HDPE), laboratory synthesis of natural rubber
from isoprene, and configurational control of polymers from terminal alkenes like
propene (e.g. pure isotactic and syndiotactic polymers).
• In the case of ethylene, rapid polymerization occurred at atmospheric pressure
and moderate to low temperature, giving a stronger (more crystalline) product
(HDPE) than that from radical polymerization (LDPE).
• For this important discovery these chemists received the 1963 Nobel Prize in
chemistry.
• Ziegler-Natta catalysts are prepared by reacting certain
transition metal halides with organometallic reagents such as
alkyl aluminum, lithium and zinc reagents.
• The catalyst formed by reaction of triethylaluminum with
titanium tetrachloride has been widely studied, but other
metals (e.g. V & Zr) have also proven effective.
• Polymerization of propylene through action of the titanium
catalyst gives an isotactic product; whereas, a vanadium
based catalyst gives a syndiotactic product.
Two broad classes of Ziegler–Natta catalysts
are employed, distinguished by their solubility:
•Heterogeneous supported catalysts based on titanium compounds are used in
polymerization reactions in combination with
cocatalysts, organoaluminum compounds such as triethylaluminium, Al(C2H5)3.
This class of catalyst dominates the industry.[1]
•Homogeneous catalysts usually based on complexes of the group 4
metals titanium, zirconium or hafnium. They are usually used in combination with a
different organoaluminum cocatalyst, methylaluminoxane (or methylalumoxane,
MAO). These catalysts traditionally contain metallocenes but also
feature multidentate oxygen- and nitrogen-based ligands.[2]
Ziegler–Natta catalysts are used to polymerize terminal alkenes (ethylene and
alkenes with the vinyl double bond):
n CH2=CHR → −[CH2−CHR]n−;
Steps of mechanism
• 1. Alkene polymerization occur at defect sites in the crystal lattice where the metal
is coordinatively unsaturated. TiCl3 unit of polymeric TiCl3 is the starting point
with a vacant coordination site.
• The alkyl aluminium, a lewis acid, alkylates the titanium atom on the surface of
solid to give a coordinatively unsaturated titanium alkyl complex which acts as a
lewis acid.
• Et2AlCl is used as cocatalyst. This titanium complex accepts pi electron density
from alkene om its vacant coordination site.
• The coordinated alkene then undergoes a migratory insertion into metal alkyl bond
. This migratory insertion provides an another coordinatively vacant site for
further coordination of another alkene and therefore lengthen the polymer chain.
• The release of the polymer from the titanium atom occurs by B-Hydrogen
elimination and then the chain is terminated.
Stereochemistry of poly-1-alkenes

• Natta first used polymerization catalysts based on titanium chlorides to

polymerize propylene and other 1-alkenes. He discovered that these
polymers are crystalline materials and ascribed their crystallinity to a
special feature of the polymer structure called stereoregularity.

isotactic

syndiotactic
• The concept of stereoregularity in polymer chains is illustrated in the picture on
the left with polypropylene.
• Stereoregular poly(1-alkene) can be isotactic or syndiotactic depending on the
relative orientation of the alkyl groups in polymer chains consisting of units
−[CH2−CHR]−, like the CH3 groups in the figure.
• In the isotactic polymers, all stereogenic centers CHR share the same
configuration. The stereogenic centers in syndiotactic polymers alternate their
relative configuration.
• A polymer that lacks any regular arrangement in the position of its alkyl
substituents (R) is called atactic.
• Both isotactic and syndiotactic polypropylene are crystalline, whereas atactic
polypropylene, which can also be prepared with special Ziegler–Natta catalysts, is
amorphous. The stereoregularity of the polymer is determined by the catalyst used
to prepare it.