On the Origin of the Distinctly Different Reactivity of Ruthenium in [MO]+/CH4 Systems (M=Fe,Ru, Os) |
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| Authors: | Dr. Xiaoyan Sun Prof. Dr. Shaodong Zhou Dr. Lei Yue Dr. Maria Schlangen Prof. Dr. Helmut Schwarz |
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| Affiliation: | 1. Institut für Chemie, Technische Universit?t Berlin, Berlin, Germany;2. Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, P.R. China |
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| Abstract: | The thermal gas‐phase reactions of [RuO]+ with methane have been explored by FT‐ICR mass spectrometry and high‐level quantum‐chemical calculations. In contrast to the previously studied [FeO]+/CH4 and [OsO]+/CH4 couples, which undergo oxygen/hydrogen atom transfers and dehydrogenation, respectively, the [RuO]+/CH4 system produces selectively [Ru(CH)2]+ and H2O, albeit with much lower efficiency. Various mechanistic scenarios were uncovered, and the associated electronic origins were revealed by high‐level quantum‐chemical calculations. The reactivity differences observed for the [MO]+/CH4 couples (M=Fe, Ru, Os) are due to the subtle interplay of the spin–orbit coupling efficiency, orbital overlap, and relativistic effects. |
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| Keywords: | gas-phase reactions methane activation quantum-chemical calculations ruthenium oxide |
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