Cobaltocene-Mediated Catalytic Hydride Transfer: Strategies for Electrocatalytic Hydrogenation

作者：Daniel P. Marron, Conor M. Galvin, Julia M. Dressel, Robert M. Waymouth · 发表于：Journal of the American Chemical Society · 年份：2024 · 被引用次数：15 · 研究领域：Asymmetric Hydrogenation and Catalysis、CO2 Reduction Techniques and Catalysts、Electrocatalysts for Energy Conversion

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 (C 5 H 5 )Co I (C 5 H 6 ) (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.