Bienenmann Roel L M, Loyo Anne Olarte, Lutz Martin, Broere Daniël L J
Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Faculty of Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
Structural Biochemistry, Bijvoet Centre for Biomolecular Research, Faculty of Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
ACS Catal. 2024 Oct 7;14(20):15599-15608. doi: 10.1021/acscatal.4c05008. eCollection 2024 Oct 18.
Copper(I) hydride complexes are typically known to react with CO 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.
氢化亚铜配合物通常已知会与一氧化碳反应形成相应的甲酸铜对应物。然而，最近观察到一些多核氢化铜具有相反的反应活性，并能催化甲酸脱氢。在此，我们报告了使用一种多核PNNP氢化铜配合物作为该反应的活性（预）催化剂。机理研究提供了对催化剂静止状态和速率决定步骤的深入了解，并确定了一种循环外物种，该物种是此反应中意外底物抑制的原因。
