Detection of transient intermediates generated from subsite analogues of [FeFe]-hydrogenases

This article reviews the application of transient techniques in the elucidation of electron, proton and photon chemistry related to the catalytic subsite of [FeFe]-hydrogenase from the perspective of research in this area carried out at the UEA and Strathclyde laboratories. The detection of mixed valence states, bridging CO intermediates, paramagnetic hydrides and coordinatively unsaturated species has both informed an understanding of the biological catalysis and stimulated the search for stable analogues of key structural motifs likely involved in turnover states.