On the assistance of the heterolytic cleavage of H2 by an
external base: a theoretical assessment
Abstract
The assistance, by a Lewis base, of the heterolytic cleavage of
co-ordinated H
2
during a σ-bond metathesis process
involving late transition-metal complexes has been analysed with the aid
of ab initio Møller–Plesset second-order
perturbation (MP2) calculations on the
[Rh(H
2
)(PH
3
)
2
(HCO
2
)]
· · ·
NH
3
model system. It is found that both the kinetics
and the thermodynamics of the metathesis process are favoured in the
presence of the amine. The structures of the various intermediates and
transition states, which show how the amine mediates the proton
transfer, are discussed.
NH
3
model system. It is found that both the kinetics
and the thermodynamics of the metathesis process are favoured in the
presence of the amine. The structures of the various intermediates and
transition states, which show how the amine mediates the proton
transfer, are discussed.
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