Diaryldichalcogenide radical cations

Ole Mallow, Monther A. Khanfar, Moritz Malischewski, Pamela Finke, Malte Hesse, Enno Lork, Timo Augenstein, Frank Breher, Jeffrey R. Harmer, Nadezhda V. Vasilieva, Andrey Zibarev, Artem S. Bogomyakov, Konrad Seppelt, Jens Beckmann

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.