CH Bond Activation by Early Transition Metal Carbide Cluster Anion MoC3− |
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| Authors: | Zi‐Yu Li Lianrui Hu Qing‐Yu Liu Prof. Dr. Chuan‐Gang Ning Prof. Dr. Hui Chen Prof. Dr. Sheng‐Gui He Prof. Dr. Jiannian Yao |
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| Affiliation: | 1. Beijing National Laboratory for Molecular Science, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P. R. China);2. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (P. R. China);3. Department of Physics, State Key Laboratory of Low‐Dimensional Quantum Physics, Tsinghua University, Beijing 100084 (P. R. China) |
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| Abstract: | Although early transition metal (ETM) carbides can activate C?H bonds in condensed‐phase systems, the electronic‐level mechanism is unclear. Atomic clusters are ideal model systems for understanding the mechanisms of bond activation. For the first time, C?H activation of a simple alkane (ethane) by an ETM carbide cluster anion (MoC3?) under thermal‐collision conditions has been identified by using high‐resolution mass spectrometry, photoelectron imaging spectroscopy, and high‐level quantum chemical calculations. Dehydrogenation and ethene elimination were observed in the reaction of MoC3? with C2H6. The C?H activation follows a mechanism of oxidative addition that is much more favorable in the carbon‐stabilized low‐spin ground electronic state than in the high‐spin excited state. The reaction efficiency between the MoC3? anion and C2H6 is low (0.23±0.05) %. A comparison between the anionic and a highly efficient cationic reaction system (Pt++C2H6) was made. It turned out that the potential‐energy surfaces for the entrance channels of the anionic and cationic reaction systems can be very different. |
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| Keywords: | carbides C H activation density functional calculations molybdenum reaction mechanisms |
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