XAFS of short-lived reduction products of structural and functional models of the [Fe–Fe] hydrogenase H-cluster

Thiolate-bridged diiron compounds that are related to the active site of the [Fe–Fe] hydrogenase enzyme have been shown to act as electrocatalysts for reduction of protons. The use of XAFS for clarification of the structures of intermediates formed following reduction of related diiron carbonyl compounds is described. These measurements allow the determination of Fe–Fe and Fe–S bond lengths with good reliability and when used in conjunction with the standard bonding models this provides a means of validating the structures proposed for longer-lived (t1/2>20s at −50 °C) reaction intermediates.