XeF₂/Fluoride Acceptors as Versatile One‐Electron Oxidants

Abstract

No phlogiston but xenon is released when XeF2 /F(-) acceptors act as new one-electron oxidants. F(-) acceptors are Lewis acids BF3 , B(C6 F5 )3 , and Al{OC(CF3 )3 }3 , and silyl derivatives TfOSiMe3 , Tf2 NSiMe3 , Me3 Si(+) B(C6 F5 )4 (-) , and Me3 Si(+) CHB11 Cl11 (-) . The anions BF4 (-) , TfO(-) , Tf2 N(-) , FB(C6 F5 )3 (-) , FAl{OC(CF3 )3 }3 (-) , B(C6 F5 )4 (-) , or CHB11 Cl11 (-) can be introduced into oxidation products of R2 E2 (E=S, Se, Te), [FeCp2 ], [(FeCpS)4 ], tetrathiafulvalene, thianthrene, and (2,4-Br2 C6 H3 )3 N.

The Me3NB12Cl11. Radical: A Strong One‐Electron Oxidizing Agent

“…Thianthrene is oxidized in a clean reaction in liquid sulfur dioxide to the purple thianthrenium radical cation, which was characterized by X‐ray diffraction (Figure b) . The thianthrenium cation is quasi planar and forms dimers in accord with previous reports . In an analogous reaction in liquid sulfur dioxide Me 3 NB 12 Cl 11 .…”

“…Thus they are often not suitable to oxidize substrates having high ionization energies, for instance, the electronegative elements. Recently, the combination of XeF 2 and a Lewis acid has been suggested as a powerful one‐electron oxidizing agent . The limitations of the existing oxidizing agents show the need for alternative fluorine‐free strong oxidizing agents.…”

Seleniranium and Telluriranium Salts

“…Thiiranium and thiirenium salts are long known. Their occurrence during the addition of sulfur electrophiles such as sulfenyl chlorides RSCl or [R 3 S 3 ] + salts to olefins and acetylenes and their structures have been described . Preparative applications have been used in sulfenyl fluorinations and sulfenyl phosphorylations of olefins.…”

Synthesis, Characterization, and Crystal Structure of a Triazine Anion Pentafluoroosmium(VI) Complex

“…The synthesis and crystal structure of other substituted benzene cations such as aniline radical cation [3] and radical cation of monocyclic arenes [4,5] have also been reported. Further research was directed toward the formation of stable radicals for several organic systems [6][7][8][9]. On the other hand, fluorine-containing compounds are important for life and material sciences [10][11][12].…”