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

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