Organometallic Chemistry in [NiFe] Hydrogenases: Synthesis of the Structural and Functional Models

Abstract

Hydrogenases catalyze reversible oxidation/reduction of molecular-hydrogen/protons in nature, and the enzymes are classified into three groups, namely, the [NiFe], [FeFe], and [Fe] hydrogenases. We herein summarize our structural and functional model studies on the [NiFe] hydrogenase. A seires of (OC)₃Fe(II)-Ni(II), (OC)₂(NC)₂Fe(II)-Ni(II), and (OC)(NC)₂Fe(II)-Ni(II) complexes bridged by thiolato ligands have been synthesized as models of the [NiFe] hydrogenase active site. The investigations of dihydrogen activation at the chalcogenido bridged Ge-Ru and W-Ru complexes, and coordinatively unsaturated Ir and Rh thiolato complexes provide clues to understand the mechanism of the [NiFe] hydrogenase function.