Diaryldichalcogenide radical cations

One-electron oxidation of two series of diaryldichalcogenides (C(6)F(5)E)(2) (13a–c) and (2,6-Mes(2)C(6)H(3)E)(2) (16a–c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF(5) and SbF(5) gave rise to the formation of thermally unstable radical cations [(C(6)F(5)S)(2)]˙(+) (14a) and [(C(6)F(5)Se)(2)]˙(+) (14b) that were isolated as [Sb(2)F(11)](–) and [As(2)F(11)](–) salts, respectively. The reaction of 13c with AsF(5) afforded only the product of a Te–C bond cleavage, namely the previously known dication [Te(4)](2+) that was isolated as [AsF(6)](–) salt. The reaction of (2,6-Mes(2)C(6)H(3)E)(2) (16a–c) with [NO][SbF(6)] provided the corresponding radical cations [(2,6-Mes(2)C(6)H(3)E)(2)]˙(+) (17a–c; E = S, Se, Te) in the form of thermally stable [SbF(6)](–) salts in nearly quantitative yields. The electronic and structural properties of these radical cations were probed by X-ray diffraction analysis, EPR spectroscopy, and density functional theory calculations and other methods.