Diaryldichalcogenide radical cations.

ABSTRACT: 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.

SUBMITTER: Mallow O 

PROVIDER: S-EPMC5588450 | biostudies-literature | 2015 Jan

REPOSITORIES: biostudies-literature