Fluorosulfates and perchlorates of xenon(II) and the salt [(FXeO)2S(O)F]+[AsF6]-

Article abstract of DOI:10.1021/ic50118a038

Each of the fluorine ligands of XeF₂ may be substituted by highly electronegative species. Interaction of XeF₂ with the appropriate molar quantity of anhydrous acid yields FXeOSO₂F (colorless, mp 36.6°), Xe(OSO₂F)₂ (pale yellow, mp 43-15°), FXeOClO₃ (colorless, mp 16.5°), Xe(OClO₃)₂ (a yellow solid, which decomposes below 0°), and FXeOSO₂CF₃ and FXeOSO₂-CH₃ (both of which are colorless solids). All of the compounds are thermodynamically unstable and the last three compounds are known to be detonators. Decomposition of the fluorosulfates provides for the synthesis of high-purity S₂O₆F₂. The acids HCl, HOSO₂Cl, and HOC(CF₃)₃ do not yield Xe derivatives and are oxidized. Vibrational spectroscopic evidence indicates that the xenon atom in the Xe(II) compounds is similarly coordinated to Xe in XeF₂ and FXeOSO₂F. Attempts to prepare [XeOSO₂F]⁺[MF₆]^- salts (M = Ru, As, Sb) have not been successful but the new cation [(FXeO)₂S(O)F]⁺ has been isolated in the [AsF₆]^- salt. Efforts to prepare [(FXe)₂L]⁺ (L^- = CF₃CO₂^-, Cl^-) resulted in oxidation of L.