Electronic communication between dithiolato-bridged diiron carbonyl and S-bridged redox-active centres

Abstract

The catalytic potential of linked redox centres is exemplified by the catalytic site of [FeFe]-hydrogenases, which feature a diiron subsite linked by a cysteinyl S atom to a 4Fe4S cube. The investigation of systems possessing similarly-linked redox sites is important because it provides a context for understanding the biological system and the rational design of abiological catalysts. The structural, electrochemical and spectroscopic properties of Fe2(CO)5(CH3C(CH2S)2CH2SPhNO2, I-bzNO2 and the aniline analogue, I-bzNH2, are described and IR spectroelectrochemical studies have allowed investigation of the reduction products and their reactions with CO and protons. These measurements have allo..