The dinuclear nickel–manganese complex [Ni(xbsms)Mn(CO)3(H2O)]+ (H2xbsms = 1,2-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)benzene) is reported as a bio-inspired mimic of the active site of NiFe hydrogenases catalyzing hydrogen evolution from trifluoroacetic acid in DMF with an overpotential requirement of 860 mV. This is higher than that displayed by Ni–Ru systems [Canaguier et al., Chem.–Eur. J., 2009, 15, 9350–9364] but similar to that found for related noble metal free Ni–Fe mimics [Canaguier et al., Chem. Commun. 2010, 46, 5876–5878]. A combined electrochemical and theoretical (DFT) study suggests a heterolytic mechanism for hydrogen evolution from a hydride derivative. The structure of the active intermediate, with a bridging hydride ligand between Ni and Mn, resembles that of the Ni–C active state of NiFe hydrogenases.
