Diaryldichalcogenide radical cations12. Issue 1 (30th October 2014)

• Record Type: Journal Article
• Authors: Mallow, Ole; Khanfar, Monther A.; Malischewski, Moritz; Finke, Pamela; Hesse, Malte; Lork, Enno; Augenstein, Timo; Breher, Frank; Harmer, Jeffrey R.; Vasilieva, Nadezhda V.; Zibarev, Andrey; Bogomyakov, Artem S.; Seppelt, Konrad; Beckmann, Jens
• Is Part Of: Chemical science. Volume 6:Issue 1(2015:Jan.)
• Page Start: 497
• Page End: 504
• Publication Date: 2014-10-30
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c4sc02964j
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : One-electron oxidation of diaryldichalcogenides is the key to the preparation of the corresponding radical cations. Abstract : One-electron oxidation of two series of diaryldichalcogenides (C6 F5 E)2 (13a–c ) and (2, 6-Mes2 C6 H3 E)2 (16a–c ) was studied (E = S, Se, Te). The reaction of13a and13b with AsF5 and SbF5 gave rise to the formation of thermally unstable radical cations [(C6 F5 S)2 ]˙ + (14a ) and [(C6 F5 Se)2 ]˙ + (14b ) that were isolated as [Sb2 F11 ] − and [As2 F11 ] − salts, respectively. The reaction of13c 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-Mes2 C6 H3 E)2 (16a–c ) with [NO][SbF6 ] provided the corresponding radical cations [(2, 6-Mes2 C6 H3 E)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.