Theoretical studies of the mechanism of catalytic hydrogen production by a cobaloxime

Our theoretical studies of the standard reduction potentials of the molecular complex [Co-II(dmgBF(2))(2)](0) (dmgBF(2) = difluoroboryldimethylglyoximate) in acetonitrile solution shed light on its electrocatalytic mechanism for hydrogen production. Three such mechanisms have been proposed, all proceeding through the formation of (CoH)-H-III. Our results indicate that the mechanism involving a (CoH)-H-II intermediate is the most likely.