Switching Site Reactivity in Hydrogenase Model Systems by Introducing a Pendant Amine Ligand.

Hydrogenases are versatile enzymatic catalysts with an unmet hydrogen evolution reactivity (HER) from synthetic bio-inspired systems. The binuclear active site only has one-site reactivity of the distal Fe atom. Here, binuclear complexes [Fe(CO)(μ-Mebdt)(P(4-CHOCH))] and [Fe(CO)(μ-Mebdt)(PPhPy)] are presented, which show electrocatalytic activity in the presence of weak acids as a proton source for the HER.