Potential-Dependent Electrocatalytic Pathways: Controlling Reactivity with pKa for Mechanistic Investigation of a Nickel-Based Hydrogen Evolution Catalyst.

A detailed mechanistic analysis is presented for the hydrogen evolution catalyst [Ni(P2(Ph)N2(Ph))2(CH2CN)][BF4]2 in acetonitrile (P2(Ph)N2(Ph) = 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane). This complex has a Ni(II/I) redox couple at −0.83 V and a Ni(I/0) redox couple at −1.03 V versus Fc(+/0). These two closely spaced redox events both promote proton reduction catalysis, each via a distinct mechanism: an electrochemical ECEC pathway and an EECC route. The EECC mechanism, operative at more negative potentials, was isolated through use of a weak acid (anilinium, pKa = 10.6 in CH3CN) to avert protonation of the singly reduced species. Electroanalytical methods and time-resolved spectroscopy were used to analyze the kinetics of the elementary steps of hydrogen evolution catalysis. The rate constant for the formation of a nickel(II)–hydride intermediate was determined via measurements of peak shift (k1 = 1.2 × 106 M(-1) s(-1)) and through foot-of-the-wave analysis (k1 = 6.5 × 106 M(-1) s(-1)). Reactivity of the isolated hydride with acid to release hydrogen and regenerate the nickel(II) complex was monitored by stopped-flow spectroscopy. Kinetics obtained from stopped-flow measurements are corroborated by current plateau analysis of the catalytic cyclic voltammograms. These kinetic data suggest the presence of an off-cycle intermediate in the reaction.