12769-73-2Relevant articles and documents
The reaction of dioxygen difluoride and sulfur dioxide. Transfer of the OOF group
Solomon, Irvine J.,Kacmarek, Andrew J.,Raney, Jack
, p. 1221 - 1224 (1968)
The reaction of dioxygen difluoride with sulfur dioxide produces mainly sulfuryl fluoride and lesser amounts of pyrosulfuryl fluoride and fluorosulfuryl hypofluorite. The mechanism of this reaction was studied using O17-tracer techniques and O17 nmr measurements. It was concluded that the sulfuryl fluoride is formed by a simple fluorination reaction. The pyrosulfuryl fluoride is formed via an FSO3· intermediate, which results in scrambling. It was concluded that fluorosulfuryl hypofluorite results via an OOF intermediate.
Silver(II) fluorosulfate: A thermally fragile ferromagnetic derivative of divalent silver in an oxa-ligand environment
Malinowski, Przemyslaw J.,Derzsi, Mariana,Mazej, Zoran,Jaglicic, Zvonko,Leszczyanski, Piotr J.,Michalowski, Tomasz,Grochala, Wojciech
, p. 2499 - 2507 (2011)
Several synthetic pathways and characterization of silver(II) fluorosulfate are reported. The title compound crystallizes in the monoclinic space group, P21/c, with a = 10.5130(4) A, b = 7.7524(3) A, c = 8.9366(4) A, β = 117.867(2)° [V = 643.88(5) A3, Z = 4, dcalcd. = 3.15 gcm-3] in a structure type related to that of AgF2. Puckered [Ag(SO3F)2] sheets are present in the crystal structure with two oxygen atoms of the fluorosulfate anions utilized for bonding within the sheet; the third oxygen atom serves as a linker to the adjacent sheet. Terminal fluorine atoms form small cavities in the structure. The S-O stretching region of the vibrational (IR and Raman) spectra is rich in bands, thus confirming the structural complexity of Ag(SO 3F)2. Ag(SO3F)2 is a soft ferromagnet with a Curie temperature of 24.8 K and it shows a single broad electron spin resonance (ESR) with g = 2.183 at T = 293 K. The intrasheet magnetic superexchange constant, J, derived from magnetization measurements, equals +1.0 meV per formula unit. Density functional theory calculations suggest that the superexchange occurs through the OO moiety of the Ag-O-S-O-Ag bridge while omitting the S atom, and the yield is J = +1.1 meV. The Coulomb-corrected local spin density approximation (LSDA+U) calculations predict a direct electronic band gap at the Fermi level of 1.05 eV. Large magnetic moments reside on O atoms attached to AgII; in consequence, Ag(SO 3F)2 is thermally unstable; at room temperature or in the presence of strong acids its dark brown crystals slowly decompose at the surface to a black mixed-valence Ag3(SO3F)4. Very fast exothermic decomposition of Ag(SO3F)2 with emission of a fluorosulfuryl radical (SO3F′·) occurs above 120 °C as confirmed by simultaneous thermogravimetric, calorimetric and evolved gas analyses. Ag(SO3F)2 exhibits a puckered sheet structure and it shows 2D ferromagnetism below 25 K; DFT methods predict it to be a magnetic semiconductor with the band gap at the Fermi level of approximately 1.05 eV.Magnetic superexchange take place through the OO moiety of the structural O-S-O bridge while omitting the sulfur atom, similarly as for related AgSO4.
Microwave, millimeterwave, and high-resolution FTIR study of the ν2=1 state of SO2F2
Merke,Heineking,Hegelund,Demaison,Margulès,Bürger
, p. 185 - 189 (2006)
Microwave and millimeterwave spectra of SO2F2 in The v2=1 state up to 450 GHz have been assigned and 174 pure rotational lines measured. The high-resolution infrared spectrum of the ν2 band (νsym SF2) centered at 849.5 cm-1 has been recorded with a resolution of 0.0024 cm-1. About 1900 rovibrational transitions with ΔKa=0 and ±2 have been assigned. Rotational and rovibrational data have been combined, and excited state parameters up to sextic centrifugal distortion constants have been obtained using a Watson type Hamiltonian in S-reduction. No perturbation has been observed, although weak B-type Coriolis interactions with ν8 may be deduced from the effective state parameters.
The preparation and characterization of SeCl3SbF6, improved syntheses of MCl3(As/Sb)F6 (M = S, Se), and the X-ray crystal structure determination of SeCl3AsF6 and a new phase of SBr3SbF6
Passmore, Jack,Cameron, T. Stanley,Boyle, Paul D.,Schatte, Gabriele,Way, Todd
, p. 1671 - 1681 (1996)
Alternative and, in some cases, improved syntheses of the salts MX3(As/Sb)F6 (M = S, Se) and SCl3(SbCl6/AlCl4) are described. In addition, the synthesis of SeCl3SbF6 is reported. The compounds were characterized by FT-Raman spectroscopy and the X-ray crystal structures of SeCl3AsF6 (also 77Se NMR)and a new phase of SBr3SbF6 were determined. Crystals of SeCl3AsF6 and SBr3SbF6 are monoclinic, space group P21/c with [values for SBr3SbF6 in brackets] a = 7.678(1) [8.137(1)] A, b = 9.380(3) [9.583(2)] A, c = 11.920(3) [12.447(2)] A, β = 98.19(2)° [97.36(1)]°, V = 849.72(3) [962.6(3)] A3, z = 4, Dx = 2.925 [3.502] Mg m-3, R = 0.0525 [0.055], and Rw = 0.0554 [0.060] for 1151 [1472] observed reflections.
Microwave, millimeter-wave, and high-resolution FTIR study of SO2F2: The v3, v7, v9 triad at 550 cm-1
Bürger,Demaison,Hegelund,Margulès,Merke
, p. 133 - 141 (2002)
The high-resolution infrared spectrum of the v3 (A1), v7 (B1), and v9 (B2) bands of SO2F2 at 551.6, 544.1, and 539.1 cm-1, respectively, has been recorded with a resolution of 0.0026 cm-1. Ca. 5500 transitions of this triad with ΔKa = 0, ±1 have been assigned. Microwave and millimeter-wave spectra up to 450 GHz of the v3 = 1, v7 = 1, and v9 = 1 states have been recorded and 499 pure rotational transitions in the triad states have been measured. Rotational and rovibrational data have been analyzed simultaneously with a model taking into account Coriolis interactions within the triad. In the fit the first order Coriolis resonance parameters were constrained to values from a scaled ab initio force field calculated in this work. Excited state parameters for the triad states up to octic centrifugal distortion constants have been obtained using the Watson Hamiltonian in S-reduction.
Ag3(SO3F)4: A rare example of a mixed-valent AgII/AgI compound showing 1D antiferromagnetism
Michalowski, Tomasz,Malinowski, Przemyslaw J.,Derzsi, Mariana,Mazej, Zoran,Jaglicic, Zvonko,Leszczyanski, Piotr J.,Grochala, Wojciech
, p. 2508 - 2516 (2011)
Dark brown AgI2AgII(SO3F) 4, known for over 30 years, is the first known example of four well-characterized mixed-valent (1+/2+) compounds of silver. It crystallizes in the monoclinic space group, P21/c, with a = 5.33670(19) A, b = 12.9486(4) A, c = 19.5976(7) A, β = 100.6407(13)°, V = 1330.95(8) A3, Z = 4 and dcalcd. = 3.59 gcm -3. Its chemical formula is best written as [AgI 2(SO3F)]+[AgII(SO3F) 3]-. AgII centres form 1D chains linked through OSO bridges that result in pronounced antiferromagnetic coupling with T N = 225 K and a superexchange coupling constant (J) of -7.5 meV per pair of coupled AgII cations. Ligand environments around Ag I and AgII differ substantially, which suggests a genuine mixed- (i.e., localized) and not intermediate-valent (i.e., delocalized) character of the title compound. Indeed, electronic absorption is not observed up to 7500 cm-1, so the intervalence charge-transfer transition across the electronic band gap must fall above 0.8 eV. The compound is stable up to a mere 75 °C, which marks the onset of its thermal decomposition to AgISO3F and the SO3F′· radical. AgI2AgII(SO3F)4 is, after AgSO4, the second-known 1D antiferromagnetic semiconducting oxa derivative of AgII. Dark brown monoclinic Ag3(SO 3F)4 shows 1D antiferromagnetism with an anomalously large superexchange coupling constant of -7.5 meV per pair of paramagnetic Ag II cations (for the spin density see the figure). One-dimensional [AgIISO3F]+ chains, linked through fluorosulfate anions into [AgII(SO3F)3] - sheets, constitute characteristic structural features responsible for magnetic behaviour.
Chlorine monofluoride. Reactions with sulfur oxides
Schack, Carl J.,Wilson, Richard D.
, p. 311 - 314 (1970)
The reactions of ClF with SOF2, SO2, and SO3 are reported. These reactions produce SOF4, ClSO2F, and ClOSO2F, respectively, in excellent yields. New characterization data for ClOSO2/s
Some reactions of pentafluorosulfur hypofluorite and trifluoromethyl hypofluorite
Pass,Roberts
, p. 1016 - 1019 (1963)
The reaction of peutafluorosulfur hypofluorite with sulfur dioxide in the liquid phase gives SF5OSO2F. Pentafluorosulfur hypofluorite reacts with sulfur tetrafluoride to give SF5OSF5, SF5OOSF5, and SF5OSF4OSF5, while a similar reaction in the presence of oxygen gives SF5OSF4OOSF5 and SF5OSF4OOSF4OSF5 as additional products. These new peroxides react with benzene to give C6H5OSF4OSF5. The reaction of trifluoromethyl hypofluorite with sulfur tetrafluoride gives CF3OSF5 as the only product. Trifluoromethyl hypofluorite, sulfur tetrafluoride, and oxygen react to give CF3OSF4OSF5, CF3OSF4OOSF5, and a compound believed to be CF3OSF4OOSF4OCF3. A reaction scheme which accounts for these products is proposed.
Chemoselective Hydro(Chloro)pentafluorosulfanylation of Diazo Compounds with Pentafluorosulfanyl Chloride
Qing, Feng-Ling,Shou, Jia-Yi,Xu, Xiu-Hua
supporting information, p. 15271 - 15275 (2021/06/08)
Pentafluorosulfanyl chloride (SF5Cl) is the most prevalent reagent for the incorporation of SF5 group into organic compounds. However, the preparation of SF5Cl often relies on hazardous reagents and specialized apparatus. Herein, we described a safe and practical synthesis of a bench-stable and easy-to-handle solution of SF5Cl in n-hexane under gas-reagent-free conditions. The synthetic application of SF5Cl was demonstrated through the unprecedented reaction with diazo compounds. The chemoselective hydro- and chloropentafluorosulfanylations of α-diazo carbonyl compounds were developed in the presence of K3PO4 or copper catalyst, respectively. These reactions provide a direct and efficient access to various α-pentafluorosulfanyl carbonyl compounds of high value for potential applications.
Reductive photo-chemical separation of the hexafluorides of uranium and molybdenum
Chemnitz, Tobias,Kraus, Florian,Petry, Winfried,Stene, Riane E.
supporting information, (2020/10/18)
Two new techniques are described for the separation of molybdenum hexafluoride (MoF6) from uranium hexafluoride (UF6). Both separation techniques utilize the differences displayed by the hexafluorides in their ability to absorb light in the near UV region. Because UF6 absorbs light in the near UV region and MoF6 does not, this observation was used to selectively reduce UF6 to uranium pentafluoride (UF5) through irradiation with 395 nm light in the presence of a suitable reducing agent. Two reducing agents were chosen for this study: gaseous, liquid, or super-critical carbon monoxide (CO) and liquid sulfur dioxide (SO2). Since MoF6 is not reduced under the reaction conditions described here, it may be removed via distillation from the uranium-containing sample after complete reduction of UF6 to solid UF5. The molybdenum- and uranium-containing samples were measured for purity through elemental analysis using microwave plasma atomic emission spectroscopy (MP-AES). Elemental analysis showed more than 98.8 % of the Mo had been removed from the U-containing samples. Further analyses of the samples were performed by X-ray powder diffraction and IR spectroscopy.
