Diaryldichalcogenide radical cations

摘要

One-electron oxidation of two series of diaryldichalcogenides (C6F5E)2 (>13a–c) and (2,6-Mes2C6H3E)2 (>16a–c) was studied (E = S, Se, Te). The reaction of >13a and >13b with AsF5 and SbF5 gave rise to the formation of thermally unstable radical cations [(C6F5S)2]˙⁺ (>14a) and [(C6F5Se)2]˙⁺ (>14b) that were isolated as [Sb2F₁₁]^– and [As₂F₁₁]^– salts, respectively. The reaction of >13c with AsF₅ afforded only the product of a Te–C bond cleavage, namely the previously known dication [Te₄]²⁺ that was isolated as [AsF₆]^– salt. The reaction of (2,6-Mes₂C₆H₃E)₂ (>16a–c) with [NO][SbF₆] provided the corresponding radical cations [(2,6-Mes₂C₆H₃E)₂]˙⁺ (>17a–c; E = S, Se, Te) in the form of thermally stable [SbF₆]^– 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.