Mechanistic Investigation into Copper(I) Hydride Catalyzed Formic Acid Dehydrogenation

Copper(I) hydride complexes are typically known to react with CO₂ to form their corresponding copper formate counterparts. However, recently it has been observed that some multinuclear copper hydrides can feature the opposite reactivity and catalyze the dehydrogenation of formic acid. Here we report the use of a multinuclear PNNP copper hydride complex as an active (pre)catalyst for this reaction. Mechanistic investigations provide insights into the catalyst resting state and the rate-determining step and identify an off-cycle species that is responsible for the unexpected substrate inhibition in this reaction.