Iron carbonyl compounds with aromatic dithiolate bridges as organometallic mimics of [FeFe] hydrogenases

Abstract Recently, substantial efforts had been made in the field of synthetic iron compounds as structural and functional models of the hydrogenase enzyme active site for the purpose of developing potential catalysts for effective and inexpensive hydrogen evolution. Amongst the bioinspired mimics, the iron carbonyl compounds bearing aromatic dithiolate bridged ligands featured the robust and tunable reductions at relatively positive potentials, and provided an appealing scaffold for easily molecular engineering, modular variation, functionalized incorporation/encapsulation of the mimetic compounds. This article surveyed and discussed a wide variety of mono-, di-, poly-nuclear iron carbonyl compounds with aromatic dithiolate bridges as synthetic “artificial” mimics of the catalytic site of [FeFe] hydrogenase in terms of structures, syntheses, redox properties, electrocatalytic characteristics in organic and aqueous solutions, and photocatalytic hydrogen evolutions. We hope that the descriptions and discussions in present review will shed light on some helpful aspects for further development of new generations of artificial catalysts for a future hydrogen economy.