Observation of the Reaction Intermediates of Methanol Dehydrogenation by Cationic Vanadium Clusters

• Published in: Angewandte Chemie International Edition Vol. 60; no. 9; pp. 4756 - 4763
• Main Authors: Hou, Gao‐Lei, Faragó, Endre, Buzsáki, Dániel, Nyulászi, László, Höltzl, Tibor, Janssens, Ewald
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 23-02-2021
• Edition: International ed. in English
• Subjects: Cations; Clusters; Cobalt; Dehydrogenation; Intermediates; Liquid nitrogen; low-pressure collision cell; mass spectrometry; Methanol; methanol dehydrogenation; Quantum chemistry; Reaction intermediates; Reaction products; Spectrometry; Vanadium; vanadium clusters; mass spectrometry; vanadium clusters; reaction intermediates; low-pressure collision cell; methanol dehydrogenation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202011109

A mass spectrometric study of the reactions of vanadium cationic clusters with methanol in a low‐pressure collision cell is reported. For comparison, the reaction of methanol with cobalt cationic clusters was studied. For vanadium, the main reaction products are fully dehydrogenated species, and partial dehydrogenation and non‐dehydrogenation species are observed as minors, for which the relative intensities increase with cluster size and also at low cluster source temperature cooled by liquid nitrogen; no dehydrogenation products were observed for cobalt clusters. Quantum chemical calculations explored the reaction pathways and revealed that the fully dehydrogenation products of the reaction between Vn+ and methanol are Vn(C)(O)+, in which C and O are separated owing to the high oxophilicity of vanadium. The partial dehydrogenation and non‐dehydrogenation species were verified to be reaction intermediates along the reaction pathway, and their most probable structures were proposed.
Strikingly different reactivity of vanadium and cobalt cationic clusters towards methanol in a low‐pressure collision cell is observed by mass spectrometry. Metastable or kinetically trapped reaction intermediates of the methanol reaction with vanadium cationic clusters are verified, and their structures are proposed by exploring the reaction pathways using density functional theory calculations.