Electrocatalytic Dihydrogen Production by an Earth-Abundant Manganese Bipyridine Catalyst

Earth-abundant manganese bipyridine complexes have been extensively studied as homogeneous electrocatalysts for proton-coupled CO2 reduction. To date, these manganese complexes have not been examined as catalysts for the reduction of other small molecules. We report electrocatalytic H2 production by [Mn(mesbpy)(CO)3(MeCN)](OTf)]. In acetonitrile, this manganese electrocatalyst displays a turnover frequency (TOF) of 5500 s(-1) at an overpotential of 0.90 V (at Ecat/2) for the reduction of protons to H2 using trifluoroacetic acid (TFA) as the acid source. These findings show the flexibility of these manganese bipyridine complexes to serve as catalysts for a variety of small molecule reductions.