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

By high-vacuum flash pyrolysis of bis(trifluoromethyl)disulfane oxide (CF3S(O)SCF3) at 400 degrees C, the elusive trifluoromethylthiyl radical (CF3S) has been efficiently generated in the gas phase. Subsequent isolation of CF3S in cryogenic matrixes (Ne, Ar, and N-2) 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 N-2 and CO and the isomerization to CF2SF, the O-2-oxidation via the intermediacy of the novel thiylperoxy radical CF3SOO has been observed.

Automated summary

Efficient generation of the elusive trifluoromethylthiyl radical (CF3S) in gas phase through high-vacuum flash pyrolysis of bis(trifluoromethyl)disulfane oxide, followed by characterization and study in cryogenic matrixes. Additionally, observation of O2-oxidation via the novel thiylperoxy radical CF3SOO and photo-induced sulfur atom transfer (SAT) and isomerization.