Release Time:2019-03-10  Hits:

Indexed by: Journal Article

Date of Publication: 2006-11-20

Journal: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

Included Journals: Scopus、SCIE

Issue: 22

Page Number: 4679-4686

ISSN: 1434-1948

Key Words: bioinorganic chemistry; density functional calculations; hydrogenases; iron; isocyanide ligands

Abstract: 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.