Catalytic Hydrogen Evolution from Mononuclear Iron(II) Carbonyl Complexes as Minimal Functional Models of the [FeFe] Hydrogenase Active Site

被引：135

作者：

Kaur-Ghumaan, Sandeep ^{[1
]}

Schwartz, Lennart ^{[1
]}

Lomoth, Reiner ^{[1
]}

Stein, Matthias ^{[2
]}

Ott, Sascha ^{[1
]}

机构：

[1] Uppsala Univ, Dept Photochem & Mol Sci, S-75120 Uppsala, Sweden

[2] Inst Theoret Studies, Mol & Cellular Modelling Grp, D-69118 Heidelberg, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2010年 / 49卷 / 43期

基金：

瑞典研究理事会;

关键词：

bioinorganic chemistry; enzyme catalysis; hydrogen production; hydrogenases; iron complexes; CRYSTAL-STRUCTURE; H-2; PRODUCTION; COORDINATION; GENERATION; REDUCTION; LIGANDS; ACIDS;

D O I：

10.1002/anie.201002719

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

How much iron does it take? Mononuclear complexes [FeII(3,6- R2bdt)(CO)2(PMe3)2] (bdt=1,2-C 6H4(S-)2; R=H, Cl) can be reversibly protonated at the sulfur ligands, can catalyze the electrochemical reduction of protons, and are thus minimal functional models of the [FeFe] hydrogenases (see scheme). DFT calculations show that cleavage of an Fe-S bond leads to the generation of a free coordination site, which is crucial for the formation of hydrides that are key intermediates in the generation of hydrogen. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：8033 / 8036

页数：4

共 20 条

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