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PGM Catalyst Handbook USA

PGM Catalyst Handbook USA

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Published by AFLAC ............
PGM Catalyst Handbook USA
PGM Catalyst Handbook USA

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Categories:Types, Research, Science
Published by: AFLAC ............ on Jul 11, 2012
Copyright:Attribution Non-commercial

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02/05/2013

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For materials to act in a catalytic, as opposed to a

stoichiometric mode, the catalyst must be recycled whilst

reactants are continuously forming product(s).

For example, a reaction with reagent 1 (R1

) reacting with

reagent 2 (R2

) in the presence of a catalyst (M) to form

product (P), where P=R1

R2

, could be written as

[M]

R1

+ R2

→P

The following scheme describes the catalytic cycle

The reaction intermediates involved in the catalytic cycle

may or may not be capable of being isolated.

The catalyst [M] is a metal atom with various chemical

species bonded to it. These are called ligands. If the

coordination number of the central metal atom is

maintained during the catalytic cycle, it may be necessary

for ligands to become detached during the course of the

reaction. This is called ligand dissociation.

In this example, the central metal atom has two ligands

(L) which dissociate and then reattach later on in the

catalytic cycle:

[ML2]

R1

P

R2

L
L

[LMR1

]

[R2

MR1
]

17

© 2008 Johnson Matthey Plc

The ligands (L) may be the same, or different, and could

include the solvent in which the reaction is being

performed. In such cases, the solvent forms part of the

catalyst cycle and hence choice of solvent can be crucial in

homogeneous catalysis.

Platinum Group Metals and all transition metals can form

such intermediates in which the nominal oxidation state

and coordination number can be systematically varied.

Transition metals have partially filled d–electron shells

which can form hybridized bonding orbitals between the

central metal atom and the ligand.

Suitable ligands are those capable of forming bonds with

σ – and π– character such as carbonyls, alkenes and

organophosphines. These ligands play a crucial role in

homogeneous catalytic chemistry.

Much academic research has focused on the interaction of

transition metal complexes with organic molecules. Many

spectroscopic techniques have been used to identify the

transient catalytic intermediates. Precise knowledge of the

intermediates and mechanisms involved can often help

process optimization.

In some cases it has been possible to construct molecular

models of reaction intermediates whose conformation will

lead to the formation of one particular product. This is

particularly applicable to the synthesis of enantiomerically-

pure isomers.

The homogeneous catalyst (or its precursor) is supplied as

a chemical compound whose characteristics, i.e. purity,

can be readily determined and controlled. It is dissolved in

the reaction medium, hence its original physical form is

less important than that of a heterogeneous catalyst.

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