Zhou Shaodong, Sun Xiaoyan, Yue Lei, Guo Cheng, Schlangen Maria, Schwarz Helmut
Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, 310027, Hangzhou, P. R. China.
Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.
Angew Chem Int Ed Engl. 2018 Nov 26;57(48):15902-15906. doi: 10.1002/anie.201809583. Epub 2018 Nov 5.
The thermal gas-phase reactions of [CeON] with methane have been explored by FT-ICR mass spectrometry and high-level quantum-chemical calculations. Nitrogen-atom transfer from the cluster ion to methane was observed as the only reaction channel. Based on computational work, the neutral molecule formed corresponds to either CH NH or CH NH. In addition to a rather weak OCe -N bond, this reaction benefits from a highly efficient intersystem crossing. Mechanistic aspects and the associated electronic origins are discussed, and a detailed comparison of [CeON] , [CeO] , [CeN] , [CeO ] , and atomic N in their reactions with CH is given.
通过傅里叶变换离子回旋共振质谱法和高水平量子化学计算研究了[CeON]与甲烷的热气相反应。观察到簇离子向甲烷的氮原子转移是唯一的反应通道。基于计算工作，形成的中性分子对应于CH₃NH或CH₂NH₂。除了相当弱的OCe-N键外，该反应还受益于高效的系间窜越。讨论了反应机理和相关的电子起源，并对[CeON]、[CeO]、[CeN]、[CeO₂]和原子N与CH₄反应进行了详细比较。
