DFT investigations of models related to the active site of [NiFe] and [Fe] hydrogenases

Density functional theory (DFT) has been recently used to explore the chemistry of models of the active site of [NiFe] and [Fe] hydrogenases, which are enzymes that catalyse the reversible oxidation of H₂. Results from recent theoretical investigations aimed at characterizing relevant intermediate species in the catalytic cycle of hydrogenases, clarifying the structural and electronic properties of the bimetallic cofactors, as well as the key factors responsible for H₂ activation, are reviewed. The role of theoretical contributions in the investigation of synthetic models related to the enzymatic metal cofactors is also discussed, showing how 'in silico' coordination chemistry can nicely complement experimental studies in the characterization of relevant species. © 2004 Elsevier B.V. All rights reserved.