Mechanism of endo-exo interconversion in η3-allyl Cp complexes:: A longstanding unresolved issue

被引：45

作者：

Ariafard, A ^{[1
]}

Bi, SW ^{[1
]}

Lin, ZY ^{[1
]}

机构：

[1] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

来源：

ORGANOMETALLICS | 2005年 / 24卷 / 10期

关键词：

D O I：

10.1021/om050161h

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Density functional theory studies of the d(6) allyl complexes CpM(CO)(eta(3)-C3H5) (M = Fe, Ru) and the d(4) allyl complex CpMo(CO)(2)(eta(3)-C3H5) show that the interconversion for CpMo(CO)(2)(eta(3)-C3H5) through the eta(3) -> eta(3) -> eta(3) pathway is intrinsically more favorable than the eta(3) -> eta(1) -> eta(3) pathway. However, the eta(3) transition states for CpM(CO)(eta(3)-C3H5) (M = Fe, Ru) are inaccessible, because one pair of the six metal d electrons has to occupy a d orbital having significant metal-Cp antibonding character in the transition structure.

引用

页码：2241 / 2244

页数：4

共 33 条

[31] Isomerism of [Ru(η3-allyl)Cl(CO)(PPh3)2] [J].