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Hidden Hydride Transfer as a Decisive Mechanistic Step in the Reactions of the Unligated Gold Carbide [AuC] + with Methane under Ambient Conditions
Author(s) -
Li Jilai,
Zhou Shaodong,
Schlangen Maria,
Weiske Thomas,
Schwarz Helmut
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201606707
Subject(s) - chemistry , hydride , natural bond orbital , fourier transform ion cyclotron resonance , reactivity (psychology) , methane , electrophile , kinetic isotope effect , carbon fibers , computational chemistry , catalysis , photochemistry , deuterium , organic chemistry , density functional theory , ion , metal , atomic physics , medicine , physics , alternative medicine , materials science , pathology , composite number , composite material
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 + /C 2 H 4 , [Au(C 2 H 2 )] + /H 2 , and [C 2 H 3 ] + /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.