Electrostatic and Charge-Induced Methane Activation by a Concerted Double C–H Bond Insertion

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• 作者：Caiyun Geng ; Jilai LiThomas Weiske ; Maria Schlangen ; Sason Shaik ; Helmut Schwarz
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：February 1, 2017
• 年：2017
• 卷：139
• 期：4
• 页码：1684-1689
• 全文大小：471K
• ISSN：1520-5126

文摘

A mechanistically unique, simultaneous activation of two C–H bonds of methane has been identified during the course of its reaction with the cationic copper carbide, [Cu–C]⁺. Detailed high-level quantum chemical calculations support the experimental findings obtained in the highly diluted gas phase using FT-ICR mass spectrometry. The behavior of [Cu–C]⁺/CH₄ contrasts that of [Au–C]⁺/CH₄, for which a stepwise bond-activation scenario prevails. An explanation for the distinct mechanistic differences of the two coinage metal complexes is given. It is demonstrated that the coupling of [Cu–C]⁺ with methane to form ethylene and Cu⁺ is modeled very well by the reaction of a carbon atom with methane mediated by an oriented external electric field of a positive point charge.