Thiolate‐Bridged Iron–Nickel Models for the Active Site of [NiFe] Hydrogenase

Hydrogenases catalyze the reversible oxidation of H2, which is crucial for the anaerobic metabolism of microorganisms. They attract growing interest in connection with H2‐based energy systems. [NiFe] hydrogenase is the most common type among the currently known hydrogenases, and its active site consists of an “organometallic” Fe–Ni complex supported by cysteinyl thiolate ligands. This review presents an overview of the synthesis, properties, and reactions of thiolate‐bridged iron–nickel complexes that model the active site of [NiFe] hydrogenase.