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 | Zendy

Zhou Shaodong | Zendy; Li Jilai | Zendy; Schlangen Maria | Zendy; Schwarz Helmut | Zendy

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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.

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