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.