PNNL

Abstract

A new Ni(II) complex, [Ni(7PPh2NH)2]2+ (7PPh2NH = 3,6-triphenyl-1-aza-3,6-diphosphacycloheptane) has been synthesized, and its electrochemical properties are reported. The 7PPh2NH ligand features an NH, ensuring properly positioned protonated amine groups (N–H+) for electrocatalysis, regardless of whether protonation occurs exo- or endo- to the metal center. The compound is an electrocatalyst for H2 production in the presence of organic acids (pKa range 10–13 in CH3CN) with turnover frequencies ranging from 160–770 s-1 at overpotentials between 320–470 mV, as measured at the half peak potential of the catalytic wave. In stark contrast to [Ni(PR2NR'2)2]2+ and other [Ni(7PPh2NR')]2+ complexes, catalytic turnover frequencies for H2 production by [Ni(7PPh2NH)2]2+ do not show catalytic rate enhancement upon the addition of H2O. This finding supports the assertion that [Ni(7PPh2NH)2]2+ eliminates the distinction between the endo- and exo-protonation isomers. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.