Electrochemical and Computational Insights into the Reduction of [Fe2(CO)6{µ-(SCH2)2GeMe2}] Hydrogenase H-Cluster Mimic

The electrochemical reduction of the complex [Fe2(CO)6{µ-(SCH2)2GeMe2}] (1) under N2 and CO is reported applying cyclic voltammetry. Reduction of complex 1 in CO saturated solutions prevents the possible release of CO from the dianion 12−, while the latter reacts with additional CO forming a spectroscopically uncharacterized product P1. This product undergoes a reversible redox process at E1/2 = −0.70 V (0.2 V∙s−1). In this report, the structure of the neutral complex 1, isomers of dianionic form of 1, and P1 are described applying DFT computations. Furthermore, we propose reaction pathways for H2 production on the basis of the cyclic voltammetry of complex 1 in presence of the strong acid CF3SO3H.