Solvent and electrolyte effects on Ni(P(R)(2)N(R')2)(2)-catalyzed electrochemical oxidation of hydrogen.

We report solvent and electrolyte effects on the electrocatalytic oxidation of H2 using Ni(P(Cy)2N(R')2)2 (R = Bn, (t)Bu) complexes. A turnover frequency of 46 s(-1) for Ni(P(Cy)2N(Bn)2)2 was obtained using 0.2 M [(n)Bu4N][BF4] in THF. A turnover frequency of 51 s(-1) was observed for Ni(P(Cy)2N(tBu)2)2 using 0.2 M [(n)Bu4N][B(C6F5)4] in fluorobenzene. These observations, in conjunction with previous studies, indicate nitrile binding inhibits catalysis supported by Ni(P(Cy)2N(Bn)2)2.