(Spectro)electrochemical and Electrocatalytic Investigation of 1,1′-Dithiolatoferrocene–Hexacarbonyldiiron

Hexacarbonyldiiron bridged by a 1,1′-dithiolatoferrocene, [Fe­(C5H4S)2{Fe­(CO)3}2] (1), was synthesized, and the electrochemistry showed reversible oxidation at the Fe­(C5H4S)2 site and quasi-reversible reduction at the hexacarbonyldiiron site. Spectroelectrochemical techniques showed reduction-induced ligand isomerization, where the thiolate ligand went from bridging to terminal and one carbon monoxide ligand moved to a quasi-bridging position; this mechanism was further supported by cyclic voltammetry simulation and density functional theory calculations. Complex 1 showed electrocatalytic activity toward hydrogen-evolving reaction