LAUSR

Abstract Modifications of the dithiolate linkers that connect the two iron atoms of the synthetic H-cluster mimics of [FeFe] hydrogenase play a significant role on tuning its physical and electrochemical properties. In this report, we describe the redox properties and the catalytic behavior of the ortho-metalated complexes having the general formula [Fe2(CO)6{к,μ-S,η2-(R)}] (R = C13H8OS, 1 and C17H20N2S, 2) in the presence and absence of acetic acid, AcOH as a proton source. Moreover, we explore the influence of substituting one CO in complex 1 by stronger electron donating, PPh3 toward the electrochemical reduction mechanism of the resulting substituted model complex [Fe2(CO)5PPh3{к,μ-S,η2-(C13H8OS)}], 3. Overall, the reduction of complexes 1-3 proceeds via simple EE mechanism (E = electron transfer) in the absence of AcOH. In Addition, all complexes show their ability to catalyze the reduction of protons and generate H2 in the presence of AcOH.