Synthesis and Single-Electron Oxidation of Bulky Bis(m-terphenyl)chalcogenides: The Quest for Kinetically Stabilized Radical Cations

Abstract

Sterically encumbered bis(m-terphenyl)chalcogenides, (2,6-Mes₂ C₆ H₃ )₂ E (E=S, Se, Te) were obtained by the reaction of the chalcogen tetrafluorides, EF₄ , with three equivalents of m-terphenyl lithium, 2,6-Mes₂ C₆ H₃ Li. The single-electron oxidation of (2,6-Mes₂ C₆ H₃ )₂ Te using XeF₂ /K[B(C₆ F₅ )₄ ] afforded the radical cation [(2,6-Mes₂ C₆ H₃ )₂ Te][B(C₆ F₅ )₄ ] that was isolated and fully characterized. The electrochemical oxidation of the lighter homologs (2,6-Mes₂ C₆ H₃ )₂ E (E=S, Se) was irreversible and impaired by rapid decomposition.

Keywords: chalcogenes; m-terphenyl; radical cations; tellurium.