53863-36-8Relevant academic research and scientific papers
Some chemistry of high oxidation state transition metal fluorides in anhydrous HF
Lucier, G.,Shen, C.,Casteel, W. J.,Chacon, L.,Bartlett, N.
, p. 157 - 164 (1995)
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
The Preparation and Characterization of Radical Cation Salts Derived from Perfluorobenzene, Perfluorotoluene, and Perfluoronaphthalene
Richardson, T. J.,Tanzella, F. L.,Bartlett, Neil
, p. 4937 - 4943 (2007/10/02)
The salts C6F6+AsF6- (yellow), C6F5CF3- (lime green), and C10F8+AsF6- (dark green) may be prepared by electron oxidation of the appropriate perfluoro aromatic molecule with O2+AsF6-.Other O2+ salts can be similarly employed as can the more strongly oxidizing transition-metal hexafluorides, but salts of the latter are more labile than their AsF- relatives.C6F6+AsF6- is a convenient electron oxidizer (C6F6AsF6+C10F8 -> C10F8AsF6+C6F6) since that which remains from the reaction decomposes at room temperature to volatile products (2C6F6AsF6 -> C6F6+1,4-C6F8+2AsF5).Magnetic susceptibilities for C6F6AsF6 and C10F8AsF6 approximate to Curie law behavior, and g values are close to free-electron values.X-ray diffraction data (single crystal) show C6F6AsF6 to be primitive rhombohedral with a0=6.60 (1) Angstroem, α=106.0 (1) deg, V=246.1 Angstreom3, Z=1, probable space group R3, and (powder data) C10F8AsF6 to be tetragonal with a0=8.27 (5) Angstroem, c0=18.57 (s) Angstroem, V=1270 Angstoem3, Z=4.Salts derived from the monocyclic perfluoro aromatics are thermally unstable but can be kept below -15 deg C.The perfluoronapthalene salts are indefinitely stable at room temperatures.All hydrolyze rapidly.The products of thermal decomposition of the hexafluoroarsenates of the monocyclic cation salts parallel the products of the attack by F-.The latter reaction products are in the molar ratios indicated by the following equations: 2C6F6+ 2F- -> C6F6+ 1,4-C6F8; 2C6F5CF3+ ->2F- -> C6F5CF3+1,3-C6F7CF3.The 1,3-C6F7CF3 isomerizes to a 1:1 mixture with 1,4-C6F7CF3 over several days in the presence of fluoro acids.Mechanisms for the formation of the dienes are discussed.
