Hydrogen Production Using Nickel Electrocatalysts with Pendant Amines: Ligand Effects on Rates and Overpotentials

A Ni-based electrocatalyst for H2 production, [Ni(8PPh2NC6H4Br)2](BF4)2, featuring eight-membered cyclic diphosphine ligands incorporating a single amine base, 1-para-bromophenyl-3,7-triphenyl-1-aza-3,7-diphosphacycloheptane (8PPh2NC6H4Br) has been synthesized and characterized. X-ray diffraction studies reveal that the cation of [Ni(8PPh2NC6H4Br)2(CH3CN)](BF4)2 has a distorted trigonal bipyramidal geometry. In CH3CN, [Ni(8PPh2NC6H4Br)2]2+ is an electrocatalyst for reduction of protons, and it has a maximum turnover frequency for H2 production of 800 s–1 with a 700 mV overpotential (at Ecat/2) when using [(DMF)H]OTf as the acid. Addition of H2O to acidic CH3CN solutions of [Ni(8PPh2NC6H4Br)2]2+ results in an increase in the turnover frequency for H2 production to a maximum of 3300 s–1 with an overpotential of 760 mV at Ecat/2. Computational studies carried out on [Ni(8PPh2NC6H4Br)2]2+ indicate the observed catalytic rate is limited by formation of nonproductive protonated isomers, diverting active catalys...