Matrix-isolated trifluoromethylthiyl radical: sulfur atom transfer, isomerization and oxidation reactions

Abstract

By high-vacuum flash pyrolysis of bis(trifluoromethyl)disulfane oxide (CF₃S(O)SCF₃) at 400 °C, the elusive trifluoromethylthiyl radical (CF₃S˙) has been efficiently generated in the gas phase. Subsequent isolation of CF₃S˙ in cryogenic matrixes (Ne, Ar, and N₂) allows a first time characterization with IR and UV-vis spectroscopy by combining with computations at the CCSD(T)/aug-cc-pV(T + d)Z level. In addition to the photo-induced sulfur atom transfer (SAT) from CF₃S˙ to N₂ and CO and the isomerization to ˙CF₂SF, the O₂-oxidation via the intermediacy of the novel thiylperoxy radical CF₃SOO˙ has been observed.