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

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journal contribution
posted on 04.01.2017 by Caiyun Geng, Jilai Li, Thomas Weiske, Maria Schlangen, Sason Shaik, Helmut Schwarz
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.