Chapter 12: Metal Complex of Hydrogenase Active Sites

This article reviews the synthesis and chemistry of complexes that are of relevance to the structure and catalysis observed at the active sites of [NiFe], [FeFe] and [Fe] hydrogenase enzymes. Both structural and functional modelling of these biosites has been accomplished using ligand design to assemble low molecular weight metal complexes incorporating polythiolate coordination at the metal centre, coupled to appropriate amine, phosphine, cyanide and CO co-ligands. Exchange of ligands and the use of alternative metal centres, particularly Ru and Co, are discussed, and recent developments leading to the incorporation of proton relays and photoactive moieties are highlighted as strategies to generate photocatalysts for hydrogen production and oxidation for use in fuel cells.