A binuclear isocyanide azadithiolatoiron complex relevant to the active site of Fe-only hydrogenases: Synthesis, structure and electrochemical properties

被引：43

作者：

Hou, Jun

Peng, Xiaojun ^{[1
]}

Liu, Jifeng

Gao, Yunling

Zhao, Xing

Gao, Shang

Han, Keli

机构：

[1] Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116012, Peoples R China

[2] Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116022, Peoples R China

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2006年 / 22期

关键词：

bioinorganic chemistry; density functional calculations; hydrogenases; iron; isocyanide ligands;

D O I：

10.1002/ejic.200600452

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

An aromatic isocynide-substituted diiron complex 5 has been synthesized as amimic for the active site of Fe-only hydrogenases. Its structure has been fully characterised by X-ray crystallography. The 4-iodophenylisocyanide ligands in 5 are in the basal positions and are nearly parallel to each other, with pi-pi stacking interactions. Four isomeric geometries of complex 5 have been optimized by DFT calculations, and the electrochemical properties of 5 have been investigated by cyclic voltammetry in the absence and presence of p-toluenesulfonic acid (HOTs). Analysis of the cyclic voltammetric curve indicates that the reduction event at about -1.43 V is electrocatalytically active to proton reduction. This potential is more positive than that of any functionalized propanedithiolatidiiron complex. (c) Woley-VCH Verlag GmbH & Co. KGaA.

引用

页码：4679 / 4686

页数：8

共 56 条

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