Gold(III) Mediated Activation and Transformation of Methane on Au1-Doped Vanadium Oxide Cluster Cations AuV2O6+

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• 作者：Zi-Yu Li ; Hai-Fang Li ; Yan-Xia Zhao ; Sheng-Gui He
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：August 3, 2016
• 年：2016
• 卷：138
• 期：30
• 页码：9437-9443
• 全文大小：522K
• 年卷期：0
• ISSN：1520-5126

文摘

Gold in the +III oxidation state (Au^III) has been proposed as a promising species to mediate challenging chemical reactions. However, it is difficult to characterize the chemistry of individual Au^III species in condensed-phase systems mainly due to the interference from the Au^I counterpart. Herein, by doping Au atoms into gas-phase vanadium oxide clusters, we demonstrate that the Au^III cation in the AuV₂O₆⁺ cluster is active for activation and transformation of methane, the most stable alkane molecule, into formaldehyde under mild conditions. In contrast, the AuV₂O₆⁺ cluster isomers with the Au^I cation can only absorb CH₄. The clusters were generated by laser ablation and mass selected to react with CH₄, CD₄, or CH₂D₂ in an ion trap reactor. The reactivity was characterized by mass spectrometry and quantum chemistry calculations. The structures of the reactant and product ions were identified by using collision-induced and 425 nm photo-induced dissociation techniques.