An Air-Stable Fe3S4 Complex with Properties Similar to Those of the HOXair State of the Diiron Hydrogenases

An Air-Stable Fe3S4 Complex with Properties Similar to Those of the HOXair State of the Diiron Hydrogenases:

Abstract

A Fe₃S₄ complex bridged by azapropanedithiolate (adt), complex 6, was prepared as a potential model of the H_OX^air state of [FeFe]-hydrogenases. Complex 6 was characterized by IR and ¹H NMR spectroscopy, and its structure was determined by X-ray crystallography. The electrochemical studies show that complex 6 is redox-active under acidic conditions, which provides insight into the catalytic mechanism. Hydrogen evolution, driven by visible light, was observed in CH₃CN/D₂O solution by online mass spectroscopy.

An air-stable Fe₃S₄ complex was prepared as a mimic of the H_OX^air state of the active site of [FeFe]-hydrogenases. Electrochemical and photoinduced hydrogen evolution is promoted by this catalyst.