Spectroelectrochemistry of hydrogenase enzymes and related compounds

The experimental approaches used to conduct IR spectroelectrochemical (SEC) studies from enzymes and inorganic compounds at ambient and elevated gas pressures are described. The application of these techniques to the study of the catalytically active site of [NiFe]- and [FeFe]-hydrogenase enzymes in their different accessible states and to the study of relevant metal complexes is reviewed. Dithiolate bridged diiron compounds provide functional models of the hydrogenases. The application of chemical, electrochemical and SEC techniques to the elucidation of the details of the electrocatalytic proton reduction is described.