Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC]+ with Methane under Ambient Conditions. (6th October 2016)

• Record Type: Journal Article
• Authors: Li, Jilai; Zhou, Shaodong; Schlangen, Maria; Weiske, Thomas; Schwarz, Helmut
• Is Part Of: Angewandte Chemie. Volume 128:Number 42(2016)
• Page Start: 13266
• Page End: 13269
• Publication Date: 2016-10-06
• Subjects: Carbid -- C-H-Bindungsaktivierung -- Gasphasenreaktionen -- Hydrid-Transfer; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201606707
• Languages: English
• ISSNs: 0044-8249

Abstract

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 + /C2 H4, [Au(C2 H2 )] + /H2, and [C2 H3 ] + /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.