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Mechanistic Investigation into Copper(I) Hydride Catalyzed Formic Acid Dehydrogenation
Roel L M Bienenmann1, Anne Olarte Loyo1, Martin Lutz2
1Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Faculty of Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Abstract:
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.
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