Use of a PCET Mediator Enables a Ni-HER Electrocatalyst to Act as a Hydride Delivery Agent

The generation of metal hydride intermediates during reductive electrocatalysis in the presence of acid most commonly leads to the hydrogen evolution reaction (HER). Redirecting the reactivity profile of such hydride intermediates toward the reduction of unsaturated substrates is an exciting opportunity in catalysis but presents a challenge in terms of catalyst selectivity. In this study, we demonstrate that a prototypical phosphine-supported Ni-HER catalyst can be repurposed toward the electrocatalytic reduction of a model substrate, methyl phenylpropiolate, via hydride transfer from a Ni^II-H when interfaced with a metallocene-derived proton-coupled electron transfer (PCET) mediator. Key to success is generation of the Ni^II-H at a potential pinned to that of the PCET mediator which is appreciably anodic of the onset of HER. Electrochemical, spectroscopic, and theoretical data point to a working mechanism where a PCET step from the metallocene-derived mediator to Ni^II generates Ni^III-H and is rate-determining; the latter Ni^III-H is then readily reduced to a Ni^II-H, which is competent for substrate reduction. Additional studies show that this tandem PCET-mediated hydride generation can afford high stereoselectivity (e.g., >20:1 Z/E using a phosphine-cobalt precatalyst with ethyl 2-heptynoate) and can also be used for the reduction of α,β-unsaturated ketones.