Catalytic hydrogen evolution from a covalently linked dicobaloxime.

A dicobaloxime in which monomeric Co(III) units are linked by an octamethylene bis(glyoxime) catalyzes the reduction of protons from p-toluenesulfonic acid as evidenced by electrocatalytic waves at -0.4 V vs. the saturated calomel electrode (SCE) in acetonitrile solutions. Rates of hydrogen evolution were determined from catalytic current peak heights (k(app) = 1100 ± 70 M(-1) s(-1)). Electrochemical experiments reveal no significant enhancement in the rate of H(2) evolution from that of a monomeric analogue: The experimental rate law is first order in catalyst and acid consistent with previous findings for similar mononuclear cobaloximes. Our work suggests that H(2) evolution likely occurs by protonation of reductively generated Co(II)H rather than homolysis of two Co(III)H units.