title: Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC]+with Methane under Ambient Conditions.
abstract: The reactivity of the cationic gold carbide [AuC]+(bearing an electrophilic carbon atom) towards methane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The product pairs generated, that is, Au+/C2H4, [Au(C2H2)]+/H2, and [C2H3]+/AuH, point to the breaking and making of C-H, C-C, and H-H bonds under single-collision conditions. The mechanisms of these rather efficient reactions have been elucidated by high-level quantum-chemical calculations. As a major result, based on molecular orbital and NBO-based charge analysis, an unprecedented hydride transfer from methane to the carbon atom of [AuC]+has been identified as a key step. Also, the origin of this novel mechanistic scenario has been addressed. The mechanistic insights derived from this study may provide guidance for the rational design of carbon-based catalysts.
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.|Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, P.R. China.
authors.forename: Jilai
authors.initials: J
authors.lastname: Li
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Shaodong
authors.initials: S
authors.lastname: Zhou
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: 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. Helmut.Schwarz@tu-berlin.de.
authors.forename: Helmut
authors.initials: H
authors.lastname: Schwarz
keywords: C−H bond activation; carbide; gas-phase reactions; hydride transfer