Formation of sulfur-centered cation radicals by photofragmentation

Article abstract of DOI:10.1016/S0040-4039(00)91715-5

The selected dialkyl dithioethers 1,5-dithiocane, 1,4-dithiepane, 1,4-dithiane, and 2,6-dithiaheptane are readily monoalkylated in nitromethane by tert-butyl 0-trifluoromethanesulfonyl-3-hydroxyperoxypropanoate 6, to give the corresponding sulfonium salt peresters 2a-c, and 3 in good yield. Laser flash photolysis of these compounds affords the known two-sulfur, three-electron stabilized cation radicals 2a, b, and 5 which were characterized by optical absorption spectroscopy.