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

Publisher Website
Google Scholar
Abstract
An aromatic isocyanide‐substituted diiron complex5has 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 in5are in the basal positions and are nearly parallel to each other, with π–π stacking interactions. Four isomeric geometries of complex5have been optimized by DFT calculations, and the electrochemical properties of5have been investigated by cyclic voltammetry in the absence and presence ofp‐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)