title: Mechanistic Aspects of the Holmium-Mediated, Reciprocal Hydrogen/Sulfur Exchange in the Gas Phase: C6 H5 CH3 +CH2 S→C6 H5 CHS+CH4.
abstract: The thermal reaction of [Ho(CH2S)](+) with toluene giving rise to [C6H5CHSHo](+) and CH4 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(CH2S)](+) 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.
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.|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: Maria
authors.initials: M
authors.lastname: Schlangen
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 activation; density functional calculations; gas-phase reactions; holmium complex; toluene