Mechanistic Aspects of the Holmium‐Mediated, Reciprocal Hydrogen/Sulfur Exchange in the Gas Phase: C₆H₅CH₃+CH₂S→C₆H₅CHS+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.