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

被引：305

作者：

Freixa, Z ^{[1
]}

van Leeuwen, PWNM ^{[1
]}

机构：

[1] Univ Amsterdam, Inst Mol Chem, NL-1018 WV Amsterdam, Netherlands

来源：

DALTON TRANSACTIONS | 2003年 / 10期

关键词：

CARBON-MONOXIDE INSERTION; PALLADIUM(II) COMPLEXES; REDUCTIVE ELIMINATION; ALTERNATING COPOLYMERIZATION; OLEFIN POLYMERIZATION; HIGH REGIOSELECTIVITY; MIGRATORY INSERTION; PHOSPHORUS LIGANDS; ACTIVE CATALYSTS; SOLID ANGLES;

D O I：

10.1039/b300322c

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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 regio-selectivity 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.

引用

页码：1890 / 1901

页数：12

共 105 条

[1] Complexes [(P-2)Rh(hfacac)] as model compounds for the fragment [(P-2)Rh] and as highly active catalysts for CO2 hydrogenation: The accessible molecular surface (AMS) model as an approach to quantifying the intrinsic steric properties of chelating ligands in homogeneous catalysis [J].