Double‐Oxygen‐Atom Transfer in Reactions of CemO2m+ (m=2–6) with C2H2 |
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| Authors: | Dr. Xun‐Lei Ding Xiao‐Nan Wu Dr. Yan‐Xia Zhao Jia‐Bi Ma Prof. Sheng‐Gui He |
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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, Zhongguancun North First Street 2, Beijing, 100190 (P.?R. China), Fax: (+86)?10‐625‐59‐373;2. Graduate School of Chinese Academy of Sciences, Beijing, 100039 (P.?R. China) |
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| Abstract: | Cerium oxide cluster cations (CemOn+, m=2–16; n=2m, 2m±1 and 2m±2) are prepared by laser ablation and reacted with acetylene (C2H2) in a fast‐flow reactor. A time‐of‐flight mass spectrometer is used to detect the cluster distribution before and after the reactions. Reactions of stoichiometric CemO2m+ (m=2–6) with C2H2 produce CemO2m?2+ clusters, which indicates a “double‐oxygen‐atom transfer” reaction CemO2m++C2H2→CemO2m?2++(CHO)2 (ethanedial). A single‐oxygen‐atom transfer reaction channel is also identified as CemO2m++C2H2→CemO2m?1++C2H2O (at least for m=2 and 3). Density functional theory calculations are performed to study reaction mechanisms of Ce2O4++C2H2, and the calculated results confirm that both the single‐ and double‐oxygen‐atom transfer channels are thermodynamically and kinetically favourable. |
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| Keywords: | cerium cluster compounds density functional calculations mass spectrometry reaction mechanisms |
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