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...

Exploring the synthetic application of sulfinyl radicals

“…Zeng's group recently isolated and characterized three fluorine-containing methylsulfinyl radicals (CF ) by combining matrix-isolation IR and UV/Vis spectroscopy with quantum chemical computations. 25,26 In cryogenic noble gas matrices, these sulfinyl radicals can isomerize to oxathiyl radicals when exposed to UV light. Natural population analyses suggest that the spin density in CH n F ( On the other hand, Baciocchi and co-workers hypothesised that the higher oxidation potential of sulfoxides over thioethers was due to the higher stability of sulfinyl radicals over thiyl radicals.…”

“…Zeng's group recently isolated and characterized three fluorine-containing methylsulfinyl radicals (CF 3 SO˙, CHF 2 SO˙, and CH 2 FSO˙) by combining matrix-isolation IR and UV/Vis spectroscopy with quantum chemical computations. 25,26 In cryogenic noble gas matrices, these sulfinyl radicals can isomerize to oxathiyl radicals when exposed to UV light. Natural population analyses suggest that the spin density in CH n F (3− n ) OS˙ is primarily localized on the sulfur atom, whereas the spin density in CH n F (3− n ) SO˙ is almost equally distributed on the sulfur and oxygen atoms (Table 1, entries 5–14).…”