Transition Metal Pyrithione Complexes (Ni, Mn, Fe, and Co) as Electrocatalysts for Proton Reduction of Acetic Acid

[Image: see text] A series of mononuclear first-row transition metal pyrithione M(pyr)(n) complexes (M = Ni(II), Mn(II), n = 2; M = Co(III), Fe(III), n = 3) have been prepared from the reaction of the corresponding metal salt with the sodium salt of pyrithione. Using cyclic voltammetry, the complexes have been shown to behave as proton reduction electrocatalysts albeit with varying efficiencies in the presence of acetic acid as the proton source in acetonitrile. The nickel complex displays the optimal overall catalytic performance with an overpotential of 0.44 V. An ECEC mechanism is suggested for the nickel-catalyzed system based on the experimental data and supported by density functional theory calculations.