Unexpected explanation for the enigmatic acid-catalysed reactivity of [Fe4S4X4]2- clusters

被引：18

作者：

Alwaaly, Ahmed ^{[1
]}

Dance, Ian ^{[2
]}

Henderson, Richard A. ^{[1
]}

机构：

[1] Newcastle Univ, Sch Chem, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England

[2] Univ New S Wales, Sch Chem, Sydney, NSW 2052, Australia

来源：

CHEMICAL COMMUNICATIONS | 2014年 / 50卷 / 37期

关键词：

S-BASED CLUSTERS; BIOLOGICAL NITROGEN-FIXATION; IRON-SULFUR PROTEINS; CHALCOGENIDE CLUSTERS; STRUCTURAL BASIS; PROTON-TRANSFER; SMALL MOLECULES; FEMO-COFACTOR; CHEMISTRY; MECHANISM;

D O I：

10.1039/c4cc00922c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Density functional calculations show that Fe-S clusters undergo unexpected large structural changes when protonated at S. Protonation of prototypical cubanoid [Fe4S4X4](2-) to [Fe4S3(SH)X-4](-) (X = CI, SR, OR) results in formation of doubly-bridging SH, severance of one Fe-S bond, and creation of a three-coordinate Fe. These findings explain previously enigmatic results concerning the reactivity of these clusters, including the rates of protonation, pKa data, and the kinetics of acid-catalysed ligand substitution.

引用

页码：4799 / 4802

页数：4

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