Fluoromethylsulfinyl radicals: spectroscopic characterization and photoisomerization via intramolecular hydrogen shift

Abstract

Two new sulfinyl radicals, CHF₂SO˙ and CH₂FSO˙, have been generated in the gas phase through homolytic cleavage of the weak S–S bonds in disulfane oxides CHF₂S(O)SCF₃ and CH₂FS(O)SCF₃ by high-vacuum flash pyrolysis (HVFP) at ca. 500 °C. The IR spectroscopy characterization of the two fluoromethylsulfinyl radicals in solid N₂ (10 K), Ar (10 K), and Ne (3 K) matrices reveals the presence of two conformers for CHF₂SO˙ (gauche and cis) and one conformer for CH₂FSO˙ (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 CHF₂OS˙ (gauche and cis) and CH₂FOS˙ (gauche) via 1,2-alkyl migration, two higher-energy carbon-centered radicals ˙CF₂SOH 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 CHF₂OS˙ and CH₂FOS˙ 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 CHF₂SO˙ and CH₂FSO˙ 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.