Facile Routes to NiF(6)(2)(-), AgF(4)(-), AuF(6)(-), and PtF(6)(-) Salts Using O(2)(+) as a Source of O(2)F in Anhydrous HF.

Abstract

O(2)(+) salts dissolved in liquid anhydrous hydrogen fluoride (aHF) at 20 degrees C or below oxidize aHF solutions of PtF(6)(2)(-) to PtF(6)(-). The parent base of O(2)(+) salts in aHF (O(2)F((solv))) generated with alkali fluoride is long-lived below -50 degrees C. An aHF solution of O(2)F((solv)) oxidizes Au(III) to Au(V) below -50 degrees C (2O(2)F((solv)) + AuF(4)(-)((solv)) --> AuF(6)(-)((solv)) +2O(2(g))). In situ generation of O(2)F((solv)) (O(2)(+)((solv)) + F(-)((solv)) --> O(2)F((solv))) with AgF(2) or NiF(2) in suspension in the aHF made basic with alkali fluoride gives AgF(4)(-) and NiF(6)(2)(-)salts. Low solubility of AAsF(6)(A = Cs, K) in aHF provides for the metathetical preparation of (O(2))(2)PdF(6) solutions in aHF. Removal of aHF, even at -60 degrees C, results in some O(2) and F(2) loss, to a composition approaching (O(2))PdF(5).