Formation of the radical anions of thiocarbonyl compounds by electron attachment to organic sulfides in glassy matrices

Reactions between the electron and various sulfides in γ-irradiated matrices at 77K have been studied to find not only the dissociative electron attachment (RCH2SR' + e- → RCH2S- + R'·), but also the reaction to produce radical anions of thiocarbonyls (RCH = S-· + R'H). The electronic absorption and ESR spectra of the radical anions, including the radical anion of thioformaldehyde as prototype of thiocarbonyls, have been recorded and analyzed in comparison with MO analyses. The formation of radical anions of thiocarbonyls depends upon the substitutents R and R' critically. A brief comparison with the oxygen analogues was also made. (author)