PNNL

Abstract

Thermodynamic data for hydride complexes of the general formula [HNi(P2RN2R’)2](BF4), 3, which have been reported previously to function as effective catalysts for the electrochemical oxidation or production of hydrogen, have been determined. Values of ?G?H+, ?G?H•, and ?G?H- have been determined for 3a where R = Cy, R’ = Bz, 3b where R = R’ = Ph, and for the new complex 3c, R = Ph, R’ = Bz. In addition, the ?G values for the heterolytic addition of hydrogen to the Ni(II) precursor complexes [Ni(P2RN2R’)2](BF4)2, 1a-c, have been determined experimentally or calculated. The data are useful for understanding the factors that control the catalytic activities observed for these complexes, and for the design of additional catalysts. Work performed at the Department of Chemistry and Biochemistry of the University of Colorado. The Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.