Issue 1, 2015

Diaryldichalcogenide radical cations


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.

Graphical abstract: Diaryldichalcogenide radical cations

Supplementary files

Article information

Article type
Edge Article
25 Sep 2014
21 Oct 2014
First published
21 Oct 2014
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2015,6, 497-504

Diaryldichalcogenide radical cations

O. Mallow, M. A. Khanfar, M. Malischewski, P. Finke, M. Hesse, E. Lork, T. Augenstein, F. Breher, J. R. Harmer, N. V. Vasilieva, A. Zibarev, A. S. Bogomyakov, K. Seppelt and J. Beckmann, Chem. Sci., 2015, 6, 497 DOI: 10.1039/C4SC02964J

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