Size Effects in Gas‐phase C−H Activation

• Published in: Chemphyschem Vol. 24; no. 6; pp. e202200769 - n/a
• Main Authors: Yuan, Bowei, Tang, Shi‐Ya, Zhou, Shaodong
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 14.03.2023
• Subjects: C−H activation; gas-phase reactions; metal-oxide clusters; Oxidation; Quantum chemistry; Selectivity; Size effects; Transition metal oxides; size effects; C−H activation; gas-phase reactions; metal-oxide clusters
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.202200769

The gas‐phase clusters reaction permits addressing fundamental aspects of the challenges related to C−H activation. The size effect plays a key role in the activation processes as it may substantially affect both the reactivity and selectivity. In this paper, we reviewed the size effect related to the hydrocarbon oxidation by early transition metal oxides and main group metal oxides, methane activation mediated by late transition metals. Based on mass‐spectrometry experiments in conjunction with quantum chemical calculations, mechanistic discussions were reviewed to present how and why the size greatly regulates the reactivity and product distribution. The size effect of the catalyst center plays an essential role in tuning the reactivity and selectivity during gas‐phase C−H activation. In this Concept, the authors review the size effects related to early‐transition‐metal‐oxide‐ and main‐group‐metal‐oxide‐mediated hydrogen atom ion and late‐transition‐metal‐mediated dehydrogenation reactions, focusing on the mechanistic origins of such effects based on structural and orbital analysis.