Cobaltocene-Mediated Catalytic Hydride Transfer: Strategies for Electrocatalytic Hydrogenation

The selective electrocatalytic hydrogenation of organics with transition metal hydrides is a promising strategy for electrosynthesis and energy storage. We report the electrocatalytic hydrogenation of acetone with a cyclopentadienone-iridium complex in a tandem electrocatalytic cycle with a cobaltocene mediator. The reductive protonation of cobaltocenium with mild acids generates (C₅H₅)Co^I(C₅H₆) (CpCo^I(CpH)), which functions as an electrocatalytic hydride mediator to deliver a hydride to cationic Ir(III) without generating hydrogen. Electrocatalytic hydride transfer by CpCo^I(CpH) to a cationic Ir species leads to the efficient (Faradaic efficiency > 90%) electrohydrogenation of acetone, a valuable hydrogenation target as a liquid organic hydrogen carrier (LOHC). Hydride–transfer mediation presents a powerful strategy to generate metal hydrides that are inaccessible by stepwise electron/proton transfer.