Fluoromethylsulfinyl radicals: spectroscopic characterization and photoisomerization via intramolecular hydrogen shift.

Two new sulfinyl radicals, CHF 2 SO˙ and CH 2 FSO˙, have been generated in the gas phase through homolytic cleavage of the weak S-S bonds in disulfane oxides CHF 2 S(O)SCF 3 and CH 2 FS(O)SCF 3 by high-vacuum flash pyrolysis (HVFP) at ca. 500 °C. The IR spectroscopy characterization of the two fluoromethylsulfinyl radicals in solid N 2 (10 K), Ar (10 K), and Ne (3 K) matrices reveals the presence of two conformers for CHF 2 SO˙ ( gauche and cis ) and one conformer for CH 2 FSO˙ ( gauche ). Upon 266 nm laser irradiation, these radicals undergo both isomerization and decomposition in the matrices. In addition to the dominant formation of the elusive oxathiyl radicals CHF 2 OS˙ ( gauche and cis ) and CH 2 FOS˙ ( gauche ) via 1,2-alkyl migration, two higher-energy carbon-centered radicals ˙CF 2 SOH and ˙CHFSOH bearing similar molecular structures to hydroperoxyalkyl radicals (˙QOOH) form via intramolecular 1,3-hydrogen shift in the two sulfinyl radicals. Additionally, the involvement of 1,3-hydrogen shift in CHF 2 OS˙ and CH 2 FOS˙ is also indicated by the observation of the fragmentation species. The identification of these radicals by matrix-isolation IR and UV-vis spectroscopy is aided by the quantum chemical calculations at the B3LYP/6-311++G(3df,3pd) level of theory. The stability of the isomers of the two sulfinyl radicals CHF 2 SO˙ and CH 2 FSO˙ has been discussed according to the experimental observations and also based on the CCSD(T)-F12a/aug-cc-pVTZ//B3LYP/6-311++G(3df,3pd) calculated energy profiles.