13637-83-7Relevant articles and documents
Acid properties of the oxytetrafluorides of molybdenum, tungsten, and uranium toward some inorganic fluoride ion donors
Bougon,Huy, T. Bui,Charpin
, p. 1822 - 1830 (1975)
The behavior of MoOF4, WOF4, and UOF4 has been studied in the presence of ion donors of various strength: FNO, ClOF3, ClF3, ClF5, and HF. For both MoOF4 and WOF4 in HF solutions, evidence for a partial ionization into Mo2O2F9- and W2O2F9- has been shown. From the equilibrium constant values, WOF4 is found to be a stronger Lewis acid than MoOF4, whereas no direct comparison with the strength of UOF4 is possible because of its quasiinsolubility in HF. Lewis acid properties of the oxytetrafluorides studied are also demonstrated by the ionic structures found for the adducts with the strong bases FNO and ClOF3. The new adducts NOMo2O2F9, NOW2O2F9, ClOF2Mo2O2F9, ClOF2MoOF5, (NO)2MoOF6, and (NO)2WOF6 were prepared. Their vibrational spectra and, for some of them, X-ray powder diffraction patterns are given. The unit cell parameters of the adducts NOMoOF5, NOWOF5, and (NO)2WOF6 have been determined. A study of the HF solutions of the nitrosyl salts has been made by Raman and 19F NMR spectroscopy. This, together with data on propylene carbonate solutions of the same adducts, allowed the identification of the species in the oxytetrafluoride-FNO-HF system. Depending on the F- concentration the anions M2O2F9-, MOF5-, and MOF62- (M = Mo or W) are formed, which are in equilibrium with the solvent. The mechanisms of these equilibria are proposed. The results obtained with the F- donor fluorinating agents indicate that ionic intermediary steps occur in the fluorination process of the oxytetrafluorides to the corresponding hexafluorides.
Reactions of chlorine fluorides and oxyfluorides with the nitrate anion and alkali-metal fluoride catalyzed decomposition of ClF5
Christe, Karl O.,Wilson, William W.,Wilson, Richard D.
, p. 675 - 677 (2008/10/08)
The binary chlorine fluorides ClF5, ClF3, and ClF, when used in an excess, all undergo facile fluorine-oxygen exchange reactions with the nitrate anion, forming FClO2, unstable FClO, and ClONO2, respectively, as the primary products. Whereas FClO3 does not react with LiNO3 at temperatures as high as 75°C, FClO2 readily reacts with either LiNO3 or N2O5 to give ClONO2 and O2 in high yield, probably via the formation of an unstable O2ClONO2 intermediate. With an excess of ClF, chlorine nitrate undergoes a slow reaction to give FNO2 and Cl2O as the primary products, followed by Cl2O reacting with ClF to give Cl2, ClF, and FClO2. The alkali-metal fluorides CsF, RbF, and KF catalyze the decomposition of ClF5 to ClF3 and F2, which can result in the generation of substantial F2 pressures at temperatures as low as 25°C.
Syntheses and properties of FOIF4O, ClOIF4O, HOIF4O, and tetrafluoroperiodates
Christe, Karl O.,Wilson, Richard D.,Schack, Carl J.
, p. 2104 - 2114 (2008/10/08)
Mixtures of cis- and trans-CsIF4O2 were prepared by the interaction of CsIO4 with either anhydrous HF, BrF5, ClF3, ClF5, or F2. The vibrational spectra of these mixtures were recorded, and partial assignments are given for cis- and trans-IF4O2-. The assignments for trans-IF4O2- were supported by a normal-coordinate analysis. The CsIF4O2 salt dissolves in CH3CN with the formation of IF4O2- anions but undergoes solvolysis in anhydrous HF with formation of HOIF4O. An improved synthesis of HOIF4O from CsIF4O2 and BiF5 in anhydrous HF is reported, and its Raman and 19F NMR spectra were recorded. The interaction of CsIF4O2 with NF4SbF6 in anhydrous HF results in solutions containing NF4+, HF2-, and HOIF4O. When standing or when pumped to dryness, these mixtures decompose to yield NF3 and the new compound FOIF4O in high yield. The latter compound, the first known example of an iodine hypofluorite, was thoroughly characterized and shown by vibrational and NMR spectroscopy to be a mixture of the cis and trans isomers. For comparison, the vibrational spectra of IF5O have also been recorded. The reaction of CsIF4O2 with ClOSO2F was shown to yield the novel compound ClOIF4O. The fluorination reactions of CsIO4, CsIF4O2, IF5O, and HOIF4O with elementary fluorine were also studied.
