Unveiling CF3SOCH3: synthesis, spectroscopic characterization, and conformational behavior of S-(trifluoromethyl)-O-(methyl) thioperoxide

Abstract

The elusive S-(trifluoromethyl)O-(methyl) thioperoxide, CF3SOCH3, and its methyl deuterated isotopologue, CF3SOCD3 were prepared for the first time via the reaction between CF3SCl and CH3OH or CD3OH, respectively. The novel compounds were thoroughly characterized using vibrational (FTIR and FT-Raman) and multinuclear NMR (1H, 19F and 13C) spectroscopies. The vibrational properties of this thioperoxide were assigned through detailed analysis of its infrared (gas-phase and matrix-isolated) and Raman spectra supported by quantum chemical calculations. CF3SOCH3 was isolated in the Ar matrix at cryogenic temperatures and exposed to broadband UV irradiation in the 225–800 nm region. The photochemical stability of the compound has thus been determined in the UV-vis range.