Issue 10, 2003

Bite angle effects in diphosphine metal catalysts: steric or electronic?

Abstract

The effects of wide bite angles of bidentate phosphine ligands on three catalytic reactions are reviewed: rhodium catalysed hydroformylation, nickel catalysed hydrocyanation, and palladium catalysed reactions of ethene, carbon monoxide and methanol leading to polyketone or methyl propanoate. The P–M–P bite angle plays a crucial role in determining the selectivity and rate in all three reactions. In this review an attempt is made to separate the mode of action into a steric and an electronic one. The regioselectivity of hydroformylation seems to be governed by steric factors, while the rate of reaction is determined by the electronic influence of the bite angle. The rates in hydrocyanation and polyketone formation were previously thought to be determined by orbital effects, but that should be questioned. Selectivity in the palladium carbonylation reaction is mainly due to steric factors.

Graphical abstract: Bite angle effects in diphosphine metal catalysts: steric or electronic?

Article information

Article type
Perspective
Submitted
09 Jan 2003
Accepted
06 Feb 2003
First published
23 Apr 2003

Dalton Trans., 2003, 1890-1901

Bite angle effects in diphosphine metal catalysts: steric or electronic?

Z. Freixa and P. W. N. M. van Leeuwen, Dalton Trans., 2003, 1890 DOI: 10.1039/B300322C

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