A Binuclear Isocyanide Azadithiolatoiron Complex Relevant to the Active Site of Fe‐Only Hydrogenases: Synthesis, Structure and Electrochemical Properties | Zendy

Hou Jun | Zendy; Peng Xiaojun | Zendy; Liu Jifeng | Zendy; Gao Yunling | Zendy; Zhao Xing | Zendy; Gao Shang | Zendy; Han Keli | Zendy

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A Binuclear Isocyanide Azadithiolatoiron Complex Relevant to the Active Site of Fe‐Only Hydrogenases: Synthesis, Structure and Electrochemical Properties

Author(s) -

Hou Jun,

Peng Xiaojun,

Liu Jifeng,

Gao Yunling,

Zhao Xing,

Gao Shang,

Han Keli

Publication year - 2006

Publication title -

european journal of inorganic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.667

H-Index - 136

eISSN - 1099-0682

pISSN - 1434-1948

DOI - 10.1002/ejic.200600452

Subject(s) - chemistry , hydrogenase , isocyanide , electrochemistry , active site , combinatorial chemistry , stereochemistry , organic chemistry , enzyme , electrode

An aromatic isocyanide‐substituted diiron complex 5 has been synthesized as a mimic for the active site of Fe‐only hydrogenases. Its structure has been fully characterized by X‐ray crystallography. The 4‐iodophenylisocyanide ligands in 5 are in the basal positions and are nearly parallel to each other, with π–π 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 propanedithiolatodiiron complex. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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