Some chemistry of high oxidation state transition metal fluorides in anhydrous HF

Article abstract of DOI:10.1016/0022-1139(94)00401-Z

The salt AgFIrF6 (AgIrF6 + 1/2F2 in AHF) is isostructural with AgFAsF6.Failure to prepare AgFOsF6 (AgOsF6 + F2 -> AgF2 + OsF6) indicates that the one-dimensional chain cation (AgF)ⁿ⁺¹n takes the electron from OsF6(1-).The Ag(2+)_(solv) ion oxidizes IrF6(1-) to IrF6 and at -78 deg C in AHF, O2 to O(1+)2 (O2 + Ag(2+) + 2AsF6(1-) -> O(1+)2AsF6(1-) + AgAsF6).This reaction is negligible at ca. 20 deg C because of the loss of translational entropy that accompanies the formation of the crystalline products.Dissolution of AgF3 in AHF with A (A = AsF5, SbF5 or BiF5) gives a solution (solv)> which oxidizes PtF6(1-) or RuF6(1-) to MF6 and O2 to O(1+)2.K2NiF6 in AHF below -60 deg C with greater than threefold molar excess of BF3 yields yellow-brown solutions (solv)> which also oxidize PtF6(1-) or RuF6(1-) to MF6.The species Ag(III)_(solv) and Ni(IV)_(solv) in AHF are oxidizers of unsurpassed power. - Keywords: Anhydrous hydrogen fluoride; Nickel hexafluoride salts; Silver tetrafluoride salts; Oxidizing power; Reactivity