SOME CHEMISTRY OF HIGH OXIDATION-STATE TRANSITION-METAL FLUORIDES IN ANHYDROUS HF

The salt AgFIrF6 (AgIrF6 + 1/2F(2) in AHF) is isostructural with AgFAsF6. Failure to prepare AgFOsF6 (AgOs-F-6 + F-2 --> AgF2 + OsF6) indicates that the one-dimensional chain cation (AgF)(n)(n+) takes the electron from OsF6-. The Ag-(solv)(2+) ion oxidizes IrF6- to IrF6 and at -78 degrees C in AHF, O-2 to O-2(+) (O-2 + Ag2+ + 2AsF(6)(-) --> O2+AsF6- + AgAsF6). This reaction is negligible at similar to 20 degrees 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 {Ag-(solv)(III)} which oxidizes PtF6- or RuF6- to MF(6) and O-2 to O-2(+). K2NiF6 in AHF below -60 degrees C with greater than threefold molar excess of BF3 yields yellow-brown solutions {Ni-(solv)(IV)} which also oxidize PtF6- or RuF6- to MF(6). The species Ag-(solv)(III) and Ni-(solv)(III) in AHF are oxidizers of unsurpassed power.