title: Electrostatic and Charge-Induced Methane Activation by a Concerted Double C-H Bond Insertion.
abstract: 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]+/CH4contrasts 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.
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Caiyun
authors.initials: C
authors.lastname: Geng
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.|Institute of Theoretical Chemistry, Jilin University , Changchun 130023, PR China.
authors.forename: Jilai
authors.identifier: 0000-0002-3363-9164
authors.initials: J
authors.lastname: Li
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Weiske
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Maria
authors.initials: M
authors.lastname: Schlangen
authors.affiliation: Institute of Chemistry and the Lise-Meitner-Minerva Center for Computational Quantum Chemistry, The Hebrew University of Jerusalem , 91904 Jerusalem, Israel.
authors.forename: Sason
authors.identifier: 0000-0001-7643-9421
authors.initials: S
authors.lastname: Shaik
authors.affiliation: Institut für Chemie, Technische Universität Berlin , Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Helmut
authors.identifier: 0000-0002-3369-7997
authors.initials: H
authors.lastname: Schwarz