Density functional studies of [(alkoxy-carbonyl)methyl]cobalt tricarbonyl triphenylphosphine complexes:: an α-ester η3-coordination

被引：8

作者：

Szabo, MJ ^{[1
]}

Szilagyi, RK ^{[1
]}

Bencze, L ^{[1
]}

机构：

[1] Univ Veszprem, Dept Organ Chem, H-8201 Veszprem, Hungary

来源：

INORGANICA CHIMICA ACTA | 2003年 / 344卷

关键词：

eta(3)-coordination; ester-cobalt interaction; chiral cobalt carbonyl phosphine complexes; density functional calculations; autosolvation-theory;

D O I：

10.1016/S0020-1693(02)01324-5

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Spectroscopic and structural data of 15 complexes with the general formula of RO(O)CCH2CO(CO)(3)PPh3 indicate a novel coordination mode of the alpha-ester group to the central cobalt atom, which was found to be crucial in the formation of configurational chirality of the ester carbon atom. Stereoselective self-assembly, elongated ester carbonyl bond lengths, reduced carbonyl stretching frequencies, and C-13/P-31 NMR coupling constants show an activated alpha-ester group compared to the uncoordinated ester or to that in a more distal position. Density functional calculations were carried out to describe the nature of this new bonding, termed earlier as 'autosolvation'. (C) 2002 Elsevier Science B.V. All rights reserved.

引用

页码：158 / 168

页数：11

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