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.
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