Diaryldichalcogenide radical cations

One-electron oxidation of two series of diaryldichalcogenides (C F E) ( ) and (2,6-Mes C H E) ( ) was studied (E = S, Se, Te). The reaction of and with AsF and SbF gave rise to the formation of thermally unstable radical cations [(C F S) ]˙ ( ) and [(C F Se) ]˙ ( ) that were isolated as [Sb F ] and [As F ] salts, respectively. The reaction of 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-Mes C H E) ( ) with [NO][SbF ] provided the corresponding radical cations [(2,6-Mes C H E) ]˙ ( ; 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.