Influence of geometry on reductive elimination of hydrocarbyl-palladium-carbene complexes

被引:37
作者
Graham, DC
Cavell, KJ
Yates, BF
机构
[1] Univ Tasmania, Sch Chem, Hobart, Tas 7001, Australia
[2] Cardiff Univ, Dept Chem, Cardiff CF10 3TB, S Glam, Wales
关键词
D O I
10.1039/b417111j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The influence of spectator ligand bite angle and the twist angle of the carbene on the reductive elimination of N-heterocyclic carbenes (NHCs) from palladium bis-phosphine complexes has been investigated using density functional theory. The spectator bite angle was found to have a significant influence on both the activation energy (E-act) and the enthalpy of reaction. Widening of the bite angle was found to lower E-act and increase the enthalpy of reaction. In contrast, rotation of the carbene with respect to the PdL2 plane was found to have little influence on E-act. At carbene twist angles approaching 0degrees however, relief of the increased steric strain provides a considerable driving force for the decomposition reaction.
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页码:1093 / 1100
页数:8
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