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 that is an active (pre)catalyst for this reaction. Mechanistic investigations provide insights into the catalyst resting state, the rate-determining step and identify an off-cycle species that is responsible for the unexpected substrate inhibition in this reaction.
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Bienenmann et al. (2024) studied this question.
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