Li Jilai, Geng Caiyun, Weiske Thomas, Schwarz Helmut
Institut für Chemie, Technische Universität Berlin, 10623, Berlin, Germany.
Institute of Theoretical Chemistry, Jilin University, 130023, Changchun, China.
Angew Chem Int Ed Engl. 2020 Jul 20;59(30):12308-12314. doi: 10.1002/anie.202001223. Epub 2020 Mar 25.
[V O] remains "invisible" in the thermal gas-phase reaction of bare [V ] with CO giving rise to [V O ] ; this is because the [V O] intermediate is being consumed more than 230 times faster than it is generated. However, the fleeting existence of [V O] and its involvement in the [V ] → [V O ] chemistry are demonstrated by a cross-over labeling experiment with a 1:1 mixture of C O /C O , generating the product ions [V O ] , [V O O] , and [V O ] in a 1:2:1 ratio. Density functional theory (DFT) calculations help to understand the remarkable and unexpected reactivity differences of [V ] versus [V O] towards CO .
在裸露的[V]与CO发生的热气相反应生成[VO]的过程中，[VO]仍然“不可见”；这是因为[VO]中间体的消耗速度比生成速度快230多倍。然而，通过用1:1的CO/CO混合物进行交叉标记实验，以1:2:1的比例生成产物离子[VO]、[VOO]和[VO]，证明了[VO]的短暂存在及其参与[V]→[VO]的化学反应。密度泛函理论（DFT）计算有助于理解[V]与[VO]对CO反应性的显著且意外的差异。
