Construction and function of [FeFe]-hydrogenase H-cluster mimics mediated by aromatic thioketone model complexes

In this study, two diiron ortho-metalated complexes derived from the reaction of phenyl(4-(phenylcarbonothioyl)phenyl)methanone (<b>1</b>) with Fe₃(CO)₁₂ have been prepared as the active site mimics of [FeFe]-hydrogenases. The resulting complexes were structurally characterized using a variety of analytical techniques (NMR, MS, IR), elemental analysis, as well as by single crystal X-ray diffraction. Moreover, the electrochemical and electrocatalytic features of these functional mimics were examined by cyclic voltammetry, revealing their potential to catalyze the reduction of protons to generate hydrogen in the presence of acetic acid (AcOH) as a proton source <i>via</i> EECC and ECEC mechanisms (E = electron transfer, C = chemical process).