Facile routes to NiF{sub 6}{sup 2{minus}}, AgF{sub 4}{sup {minus}}, AuF{sub 6}{sup {minus}}, and PtF{sub 6}{sup {minus}} salts using O{sub 2}{sup +} as a source of O{sub 2}F in anhydrous HF
- Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.
O{sub 2}{sup +} salts dissolved in liquid anhydrous hydrogen fluoride (aHF) at 20 C or below oxidize aHF solutions of PtF{sub 6}{sup 2{minus}} to PtF{sub 6}{sup {minus}}. The parent base of O{sub 2}{sup +} salts in aHF (O{sub 2}F{sub (solv)}) generated with alkali fluoride is long-lived below {minus}50 C. An aHF solution of O{sub 2}F{sub (solv)} oxidizes Au(III) to Au(V) below {minus}50 C (20{sub 2}F{sub (solv)} + AuF{sub 4}{sup {minus}}{sub (solv)} {yields} AuF{sub 6}{sup {minus}}{sub (solv)} + 2O{sub 2(g)}). In situ generation of O{sub 2}F{sub (solv)} (O{sub 2}{sup +}{sub (solv)} + F{sup {minus}}{sub (solv)} {yields} O{sub 2}F{sub (solv)}) with AgF{sub 2} or NiF{sub 2} in suspension in the aHF made basic with alkali fluoride gives AgF{sub 4}{sup {minus}} and NiF{sub 6}{sup 2{minus}} salts. Low solubility of AAsF{sub 6}(A = Cs, K) in aHF provides for the metathetical preparation of (O{sub 2}){sub 2}PdF{sub 6} solutions in aHF. Removal of aHF, even at {minus}60 C, results in some O{sub 2} and F{sub 2} loss, to a composition approaching (O{sub 2})PdF{sub 5}.
- Sponsoring Organization:
- USDOE, Washington, DC (United States); National Science Foundation, Washington, DC (United States)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 653424
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 15 Vol. 37; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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