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.
Original language | English |
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Pages (from-to) | 15599-15608 |
Number of pages | 10 |
Journal | ACS Catalysis |
Volume | 14 |
Issue number | 20 |
DOIs | |
Publication status | Published - 18 Oct 2024 |
Bibliographical note
Publisher Copyright:© 2024 The Authors. Published by American Chemical Society.
Funding
Sander de Vos is gratefully acknowledged for his help in setting up the online hydrogen GC measurements. We would like to thank Bert Klein Gebbink for his input on the manuscript. The work in this paper was supported by The Netherlands Organization of Scientific Research (VI.Veni.192.074 to D.L.J.B.). The X-ray diffractometer has been financed by The Netherlands Organization for Scientific Research (NWO).
Funders | Funder number |
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Nederlandse Organisatie voor Wetenschappelijk Onderzoek | VI.Veni.192.074 |
Keywords
- copper
- dehydrogenation
- dinuclear
- formic acid
- homogeneous catalysis
- mechanistic investigation