Electrocatalytic proton reduction catalyzed by a dimanganese disulfide carbonyl complex containing a redox-active internal disulfide bond

Abstract

A dimanganese hexacarbonyl complex [(Mn(CO)₃)₂(μ-SC₆H₄-o-S-S-C₆H₄-o-μ-S-)] containing an elongated disulfide bond electrocatalyses proton reduction at moderate overpotentials of 0.55 to 0.65 V. Cyclic voltammetric, infrared spectroscopy and computational studies suggest that the redox-active sulfur atoms of the disulfide bond serve as the initial reduction site.