Molecular orbital analysis of anomalous trans effect in cobalamins

被引：22

作者：

Andruniow, T

Kuta, J

Zgierski, MZ

Kozlowski, PM ^{[1
]}

机构：

[1] Univ Louisville, Dept Chem, Louisville, KY 40292 USA

[2] Natl Res Council Canada, Steacie Inst Mol Sci, Ottawa, ON K1A 0R6, Canada

来源：

CHEMICAL PHYSICS LETTERS | 2005年 / 410卷 / 4-6期

关键词：

D O I：

10.1016/j.cplett.2005.04.111

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Density functional theory has been applied to the analysis of N-B-Co-C-R interligand bonding in octahedral complexes of Co-III. Employing B-[Co-III(corrin)]-R+ models, it is shown that a change in the electron donating (or withdrawing) character of alkyl ligands (R) lengthens (or shortens) both interligand Co-CR and Co-N-B bonds in accordance with the anomalous (or inverse) trans effect. Six molecular orbitals are required for the succinct description of this phenomenon, which lies in an unusual combination of a poor sigma/pi-donor of the base (B) and an unusually strong sigma-donor of the alkyl group (R). (c) 2005 Elsevier B.V. All rights reserved.

引用

页码：410 / 416

页数：7

共 26 条

[1] Theoretical analysis of electronic absorption spectra of vitamin B12 models [J].