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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)