Gas phase chemistry of α-thio carbanions

Abstract

Proton abstraction from CH3SCH3 and C6H5SCH3 in the gas phase has been studied by the use of Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry. The gas phase acidity of CH3SCH3 is reported to be [Formula: see text]. The methyl group in C6H5SCH3 is observed to be the most acidic position. The gas phase acidity of this group is determined to be [Formula: see text]. The structure and reactivity of the [M – H]− ions from CH3SCH3 and C6H5SCH3 are probed by studying their reactions with various molecules. Rate constants are reported for the reactions of CH3SCH2− – and several other nucleophiles – with CH3Cl, CH3Br, and HCO2CH3.