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Mechanistic Aspects of the Holmium‐Mediated, Reciprocal Hydrogen/Sulfur Exchange in the Gas Phase: C 6 H 5 CH 3 +CH 2 S→C 6 H 5 CHS+CH 4
Author(s) -
Zhou Shaodong,
Li Jilai,
Schlangen Maria,
Schwarz Helmut
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600061
Subject(s) - reactivity (psychology) , chemistry , hydrogen , fourier transform ion cyclotron resonance , toluene , carbon monoxide , mass spectrometry , sulfur , density functional theory , hydrogen atom abstraction , resonance (particle physics) , hydrogen atom , analytical chemistry (journal) , computational chemistry , group (periodic table) , atomic physics , physics , catalysis , organic chemistry , medicine , alternative medicine , pathology , chromatography
The thermal reaction of [Ho(CH 2 S)] + with toluene giving rise to [C 6 H 5 CHSHo] + and CH 4 has been investigated using Fourier‐transform ion cyclotron resonance (FT‐ICR) mass spectrometry complemented by density functional theory (DFT) calculations. The high reactivity of [Ho(CH 2 S)] + which is in distinct contrast with the non‐reactivity of “bare” Ho + has its origin in the presence of a carbon‐centered radical; the latter initiates hydrogen‐atom abstraction from the methyl group of toluene as the first step of a sequence of hydrogen and sulfur transfer mediated by cationic holmium.