Diaryldichalcogenide radical cations

One-electron oxidation of two series of diaryldichalcogenides (CFE) (13a-c) and (2,6-MesCHE) (16a-c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF and SbF gave rise to the formation of thermally unstable radical cations [(CFS)] (14a) and [(CFSe)] (14b) that were isolated as [SbF] and [AsF] salts, respectively. The reaction of 13c with AsF afforded only the product of a Te-C bond cleavage, namely the previously known dication [Te] that was isolated as [AsF] salt. The reaction of (2,6-MesCHE) (16a-c) with [NO][SbF] provided the corresponding radical cations [(2,6-MesCHE)] (17a-c; E = S, Se, Te) in the form of thermally stable [SbF] 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. This journal i