S42- rings, disulfides, and sulfides in transition-metal complexes:: The subtle interplay of oxidation and structure

被引：37

作者：

Mealli, Carlo ^{[2
]}

Ienco, Andrea ^{[2
]}

Poduska, Anne ^{[1
]}

Hoffmann, Roald ^{[1
]}

机构：

[1] Cornell Univ, Baker Lab, Dept Chem & Chem Biol, Ithaca, NY 14853 USA

[2] ICCOM, CNR, I-50019 Florence, Italy

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2008年 / 47卷 / 15期

关键词：

density functional calculations; disulfide coupling; electronic structure; Jahn-Teller distortion; molecular orbital analysis;

D O I：

10.1002/anie.200705296

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical Equation Presented) Coming together, breaking apart: A theoretical analysis of the oxidative coupling of two metal-coordinated disulfide species to a S42- rectangle provides an opening to a reexamination of a number of compounds hitherto considered to be disulfide complexes. An electronic framework helps explain how the nature of the metal controls inner redox processes and the alternative stabilization of S 42- or 2S22- (or S2-) species (see scheme). © 2008 Wiley-VCH Verlag GmbH & Co. KGaA.

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收藏

页码：2864 / 2868

页数：5

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