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The fluorinating and oxide scavenging ability of XeF/sub 6/ have been studied by bringing XeF/sub 6/ into interaction with oxide-fluoride compounds of the third-transition-series elements (W, Re and Os) and uranium, in their highest oxidation states. A/sup +/MOF/sub 5//sup -/ and A/sup +/M/sub 2/O/sub 2/F/sub 9//sup -/ (A = K or Cs, M = W or U) were converted to A/sup +/MF/sub 7//sup -/ by XeF/sub 6/, but the rhenium and osmium compounds, K/sup +/ReO/sub 2/F/sub 4//sup -/ and XeF/sub 5//sup +/OsO/sub 3/F/sub 3//sup -/, resisted interaction with XeF/sub 6/. Strong interactions between XeF/sub 2/ or KrF/sub 2/ and the solvent have been observed for their solutions in anhydrous HF. Both XeF/sub 2/ and KrF/sub 2/ are seen to be effective in breaking up the polymeric (HF)/sub n/ chains. Only weak interactions occur between cations and anions of KrF/sup +/AuF/sub 6//sup -/ and Kr/sub 2/F/sub 3//sup +/AuF/sub 6//sup -/ in HF. The AuF/sub 6//sup -/ anions are slightly distorted from O/sub h/ symmetry. Kr/sub 2/F/sub 3//sup +/ cations in HF have the same dissymmetric V-shape which occurs in crystalline salts. A low-temperature orthorhombic form, ..beta..-ReF/sub 6//sup +/SbF/sub 6//sup -/, a high-temperature rhombohedral form, ..cap alpha..-ReF/sub 6//sup +/SbF/sub 6//sup -/, andmore » a ReF/sub 6//sup +/AuF/sub 6//sup -/ have been prepared. These compounds possess only kinetic stability at ambient temperature and at approx. 20/sup 0/C are best represented as ReF/sub 6//sup +/ReF/sub 7/MF/sub 6//sup -/MF/sub 5/. Thermochemical energy evaluations indicate that the ionization potential of ReF/sub 6/ is 261 kcal mole/sup -1/ and that the fluoride-ion affinity of ReF/sub 6//sup +/ is -214 kcal mole/sup -1/. This is more exothermal than the corresponding process for IF/sub 6//sup +/ (-208 kcal mole/sup -1/). In contrast, ReOF/sub 5/ is shown to be a better fluoro-base than IOF/sub 5/ and also is a better base than ReF/sub 7/. ReOF/sub 4//sup +/MF/sub 6//sup -/ (M = Sb, Au and As) salts are of higher thermal stability than their ReF/sub 6//sup +/MF/sub 6//sup -/ analogues.« less

Application of powerful oxidizers in the synthesis of new high-oxidation state actinide and related species