13709-32-5Relevant academic research and scientific papers
Synthesis and characterization of uranium(V) fluoride fluorosulfates and uranium(V) oxyfluorosulfate: UF3(SO3F)2, UF(SO3F)4, and UO(SO3F)3
Masson,Naulin,Charpin,Bougon
, p. 1858 - 1861 (1978)
The new uranium(V) fluoride fluorosulfate compounds UF3(SO3F)2 and UF(SO3F)4 and uranium(V) oxyfluorosulfate UO(SO3F)3 have been synthesized. UF3(SO3F)2, a pale green solid, resulted from the reaction of UF5 and S2O6F2 in CFCl3 at 40°C for 20 days; under these conditions the solvent also reacted and was partly transformed into CFCl2OSO2F and CF2Cl2. The beige solid UF(SO3F)4 was prepared by mixing UF6 and SO3 in CFCl3 at low temperature (3F)3, a tetragonal gray-beige solid. These three compounds were characterized by chemical analysis. Their thermal stabilities and vibrational and electronic spectra are also reported. The +5 oxidation state of uranium was confirmed by magnetic susceptibility measurements. Despite several attempts under different conditions, no uranium(VI) fluorosulfate or fluoride fluorosulfate was obtained.
Synthesis and characterization of the difluorotris(fluorosulfate) of uranium(V): UF2(SO3F)3
Wilson,Naulin,Bougon
, p. 2252 - 2257 (1977)
A new U(V) compound, UF2(SO3F)3, has been synthesized by the reaction of UF6 and SO3 in both the gaseous phase and CFCl3 solution. This leads to a blue-green solid, the x-ray powder diffraction pattern of which has been recorded. Its oxidation state has been deduced from chemical analysis, the electronic absorption spectrum, and magnetic measurements. The environment around uranium is discussed from Raman and infrared spectra recorded at ambient and liquid nitrogen temperatures.
Homoleptic, σ-bonded octahedral [M(CO)6]2+ cations of iron(II), ruthenium(II), and osmium(II): Part 1: Syntheses, thermochemical and vibrational characterizations, and molecular structures as [Sb2F11]- and [SbF6]- salts. A comprehensive, comparative study
Bernhardt, Eduard,Bach, Christian,Bley, Bianca,Wartchow, Rudolf,Westphal, Ulrich,Sham, Iona H.T.,Von Ahsen, Britta,Wang, Chanqing,Willner, Helge,Thompson, Robert C.,Aubke, Friedhelm
, p. 4189 - 4205 (2005)
Homoleptic octahedral, superelectrophilic σ-bonded metal carbonyl cations of the type [M(CO)6]2+ (M = Ru, Os) are generated in the Bronsted-Lewis conjugate superacid HF/SbF5 by reductive carbonylation of M(SO3F)3 (M = Ru, Os) or OsF6. Thermally stable salts form with either [Sb2F 11]- or [SbF6]- as anion, just as for the previously reported [Fe(CO)6]2+ cation. The latter salts are generated by oxidative (XeF2) carbonylation of Fe(CO)5 in HF/SbF5. A rationale for the two diverging synthetic approaches is provided. The thermal stabilities of [M(CO) 6][SbF6]2 salts, studied by DSC, range from 180 °C for M = Fe to 350 °C for M = Os before decarbonylation occurs. The two triads [M(CO)6][SbF6]2 and [M(CO) 6][Sb2F11]2 (M = Fe, Ru, Os) are extensively characterized by single-crystal X-ray diffraction and vibrational and 13C NMR spectroscopy, aided by computational studies of the cations. The three [M(CO)6][SbF6]2 salts (M = Fe, Ru, Os) crystallize in the tetragonal space group P4/mnc (No. 128), whereas the corresponding [Sb2F11]- salts are monoclinic, crystallizing in space group P21/n (No. 14). In both triads, the unit cell parameters are nearly invariant of the metal. Bond parameters for the anions [SbF6]- and [Sb 2F11]- and their vibrational properties in the two triads are completely identical. In all six salts, the structural and vibrational properties of the [M(CO)6]2+ cations (M = Fe, Ru, Os) are independent of the counteranion and for the most part independent of M and nearly identical. Interionic C...F contacts are similarly weak in all six salts. Metal dependency is noted only in the 13C NMR spectra, in the skeletal M-C vibrations, and to a much smaller extent in some of the C-O stretching fundamentals (A1g and T1u). The findings reported here are unprecedented among metal carbonyl cations and their salts.
METHODS OF MAKING HALOGENATED FLUORINATED ETHER-CONTAINING COMPOUNDS
-
Paragraph 0087-0088, (2016/06/28)
Described herein are three methods for making halogenated fluorinated ether-containing compounds using a fluorinated olefin or hexafluoropropylene oxide.
Evidences for a new ultraviolet absorption band of the FSO3 radical
Cobos,Croce
, p. 897 - 909 (2008/10/09)
An unpublished absorption band of the fluorosulphate radical, FSO 3, based on earlier experiments of Schumacher and co-workers (Z. Phys. Chem. NF 42 (1964) 174) and detailed calculations of the whole FSO 3 spectra based on the time-dependent (TD) generalization of the density functional theory (DFT), TD-DFT, are reported. Part of this band, that increases in intensity at wavelengths below 275 nm, has been extracted from an absorption spectrum taken from equilibrated mixtures of FSO3 with the dimer FS(O2)OO(O2)SF at 403 K. A set of thirteen exchange-correlation hybrid functionals combined with the 6-311+G(3df) basis set predict an intense absorption band centred at 256±10 nm in very good agreement with the experimental observations. Another significant band peaked at 184±10 nm was also found. The calculations reproduce accurately the position of the maximum and the experimental oscillator strength of the well-known visible FSO3 band system. by Oldenbourg Wissenschaftsverlag.
Cationic carbonyl complexes of rhodium(I) and rhodium(III): Syntheses, vibrational spectra, NMR studies, and molecular structures of tetrakis(carbonyl)rhodium(I) heptachlorodialuminate and -gallate, [Rh(CO)4][Al2Cl7] and [Rh(CO)4][Ga2Cl7]
Von Ahsen, Britta,Bach, Christian,Berkei, Michael,Kockerling, Martin,Willner, Helge,Hagele, Gerhard,Aubke, Friedhelm
, p. 3801 - 3814 (2008/10/08)
Dimeric rhodium(I) bis(carbonyl) chloride, [Rh(CO)2(μ-Cl)]2, is found to be a useful and convenient starting material for the syntheses of new cationic carbonyl complexes of both rhodium(I) and rhodium(III). Its reaction with the Lewis acids AlCl3 or GaCl3 produces in a CO atmosphere at room temperature the salts [Rh(CO)4][M2Cl7] (M = Al, Ga), which are characterized by Raman spectroscopy and single-crystal X-ray diffraction. Crystal data for [Rh(CO)4][Al2Cl7]: triclinic, space group P1 (No. 2); a = 9.705(3), b = 9.800(2), c = 10.268(2) A; α = 76.52(2), β = 76.05(2), γ = 66.15(2)°; V = 856.7(5) A3; Z = 2; T = 293 K; R1 [I > 2σ(I)] = 0.0524, wR2 = 0.1586. Crystal data for [Rh(CO)4][Ga2Cl7]: triclinic, space group P1 (No. 2); a = 9.649(1), b = 9.624(1), c = 10.133(1) A; α = 77.38(1), β = 76.13(1), γ = 65.61(1)°; V = 824.4(2) A3; Z = 2; T = 143 K; R1 [I > 2σ(I)] = 0.0358, wR2 = 0.0792. Structural parameters for the square planar cation [Rh(CO)4]+ are compared to those of isoelectronic [Pd(CO)4]2+ and of [Pt(CO)4]2+. Dissolution of [Rh(CO)2Cl]2 in HSO3F in a CO atmosphere allows formation of [Rh(CO)4]+(solv). Oxidation of [Rh(CO)2Cl]2 by S2O6F2 in HSO3F results in the formation of ClOSO2F and two seemingly oligomeric RH(III) carbonyl fluorosulfato intermediates, which are easily reduced by CO addition to [Rh(CO)4]+(solv). Controlled oxidation of this solution with S2O6F2 produces fac-Rh(CO)3(SO3F)3 in about 95% yield. This RH(III) complex can be reduced by CO at 25 °C in anhydrous HF to give [Rh(CO)4]+(solv); addition of SbF5 at -40 °C to the resulting solution allows isolation of [Rh(CO)4][Sb2F11]2, which is found to have a highly symmetrical (D4h) [Sb2F11]- anion. Oxidation of [Rh(CO)2Cl]2 in anhydrous HF by F2, followed in a second step by carbonylation in the presence of SbF5, is found to be a simple, straightforward route to pure [Rh(CO)5Cl][Sb2F11]2, which has previously been structurally characterized by us. All new complexes are characterized by vibrational and NMR spectroscopy. Assignment of the vibrational spectra and interpretation of the structural data are supported by DFT calculations.
Crystal and molecular structure and Raman and 127I M?ssbauer spectra of iodine(III) bis(fluorosulfate) iodide, I(OSO2F)2I
Birchall,Denes,Faggiani,Frampton,Gillespie,Kapoor,Vekris
, p. 1527 - 1530 (2008/10/08)
Iodine is oxidized by peroxodisulfuryl difluoride, S2O6F2, to give I(OSO2F)2I. Crystals are orthorhombic, space group P212121, with a = 5.511 (1) ?, b = 12.054 (2) ?, c = 13.573 (3) ?, V = 901.8 (3) ?3, and Dcalc = 3.33 g cm-3 for Z = 4. The structure was solved by means of Patterson functions and refined by least squares to final agreement indices of R1 = 0.0353 and R2 = 0.0374 for 1600 independent reflections. There are three primary bonds to the central iodine, I(1), (I(1)-OSO2F = 2.086 (7) and 2.258 (7) ?; I(1)-I(2) = 2.676 (1) ?), which create a distorted T-shaped AX3E2 geometry. The second iodine, I(2), has a primary bond to I(1) and a strong intermolecular secondary I(2)-O bond of length 2.655 (8) ? to one of the fluorosulfate groups that is colinear with the primary bond, giving an AXYE3 geometry about I(2). The Raman spectrum of the solid and the 127I M?ssbauer spectrum are in full agreement with the structure found.
Pressure and Temperature Dependence of the Reaction F+FSO3+M->FSO2OF+M
Cobos, A. E. Croce de,Cobos, C. J.,Castellano, E.
, p. 274 - 278 (2007/10/02)
The kinetics of the reaction F+FSO3+M->FSO2OF+M (1) has been studied by using an ArF excimer laser flash photolysis/visible absorption technique to monitor the disappearance of FSO3 radicals.He, N2, and SF6 were used as bath gases in pressures ranging from 5 to 600 Torr at 298 K; CF4 was used in the same pressures between 298 and 378 K.Reaction 1 was found to be in the falloff region between second- and third-order kinetics.The following limiting high- and low-pressure recombination rate constants have been determined at 298 K: krec,=(7.6+/-1.0)*10-11 cm3 molecule-1 s-1, krec,0=(4.1+/-0.5)*10-28, (5.2+/-0.7)*10-28, (1.1+/-0.2)*10-27, and (1.3+/-0.2)*10-27 cm3 molecule-1 s-1. krec, and krec,0 showed a temperature dependence of T0.23 and T-3.1 (M=CF4), respectively.With the krec, data and the known values of the high-pressure rate constant for FSO2OF thermal decomposition, the equilibrium constant and the thermodynamical parameters of the system were obtained.An analysis of the krec,0 with respect to energy-transfer properties was performed.In terms of the canonical version of the statistical adiabatic channel model, the krec, values lead to α/β=0.49 for the ratio between the looseness and the Morse parameters.Specific rate constants derived from our experiments are also discussed.
A Modified Method for the Electrolytic Preparation of Bis(fluorosulphuryl) Peroxide
Singh, Sukhjinder,Verma, Rajendar D.
, p. 51 - 53 (2007/10/02)
A modified method for the electrolytic preparation of bis(fluorosulphuryl) peroxide, S2O6F2, has been perfected.In the proposed method a current efficiency of about 92percent has been achieved for a cell operating at -8 deg C with platinum electrodes in an electrolyte containing about three mol fluorosulphuric acid per mol of potassium fluorosulphate.Potassium fluorosulphate combines with fluorosulphuric acid to form the compound KSO3F*3HSO3F, which melts at -10 deg C.
Sulfur oxyfluoride derivatives. III
Ruff,Merritt
, p. 1219 - 1221 (2008/10/08)
The reaction of S2O6F2 with the anions CF3O-, SF5O-, -N(SO2F)2, and (NO2)2CCN- produced the corresponding covale
