期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 15, 期 4, 页码 1148-1153出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2cp43544f
关键词
-
资金
- Euskal Herriko Unibertsitatea (the University of the Basque Country)
- Gipuzkoako Foru Aldundia (the Provincial Government of Guipuzkoa)
- Eusko Jaurlaritza (the Basque Government) [GIC 07/85 IT-330-07]
- Spanish Office for Scientific Research [CTQ2011-27374]
- ERC [209842-MATRIX]
The activation of methane and its subsequent conversion into more valuable feedstocks under ambient conditions are regarded as one of the major challenges in contemporary catalysis, due to its thermodynamically strong and kinetically inert C-H bond. Several enzymes and synthetic bioinorganic systems perform the activation of C-H bonds in methane and small hydrocarbons, mediated by transition metal mononuclear centers. Among them, monocopper cores and, in particular, CuO+ and CuOH+ have been suggested as efficient catalytic centers; this activity has not been experimentally proven until very recently, mainly due to the difficulty to produce sufficient amounts of active species to demonstrate the bond activation processes. The theoretical study presented here provides a thorough quantum chemical description of the activity of both species, together with molecular level insight into the elementary steps of the experimentally observed reactions. Post-HF (CCSD(T), CASPT2) and Density Functional Theory (DFT) methods have been used to unravel detailed electronic and mechanistic aspects of the reaction paths. Our study reveals the decisive role of the oxygen-centered radical in the reactivity of both species, and the improvement of the reactivity as a result of the protonation of the active species.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据