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7787-71-5Relevant articles and documents
PbF[Br2F7], a Fluoridobromate(III) of a p-Block Metal
Bandemehr, Jascha,Sachs, Malte,Ivlev, Sergei I.,Karttunen, Antti J.,Kraus, Florian
, p. 64 - 70 (2020)
The compound PbF[Br2F7] represents the first fluoridobromate(III) of a p-block element. It was synthesized in form of needle-shaped crystals among its colorless powder from the direct reaction of PbF2 with BrF3. Powder X-ray diffraction, IR and Raman spectroscopy show that it was obtained in almost pure form with Pb3F8 and Pb2F6 as by-products. The single crystal structure was determined by X-ray diffraction. PbF[Br2F7] crystallizes in space group P21/c (No. 14) with a = 4.3698(3), b = 13.3767(7), c = 12.0836(8) ?, β = 97.509(5)°, V = 700.27(8) ?3, Z = 4 at T = 100 K. PbF[Br2F7] decomposes above 50 °C due to loss of BrF3 and pure PbF2 remains. Quantum chemical calculations were performed on the crystal structure of the compound to assign the bands of the vibrational spectra and to obtain electron density difference maps that visualize the electron density around the Pb atoms. CHARDI calculations support the assignment of the oxidation states +II, +III, and –I to the Pb, Br, and F atoms, respectively.
The Interhalogen Cations [Br2F5]+ and [Br3F8]+
Ivlev, Sergei I.,Karttunen, Antti J.,Buchner, Magnus R.,Conrad, Matthias,Kraus, Florian
, (2018)
The synthesis and characterization of unique polyhalogen cations containing μ-bridging fluorine atoms are reported. The [Br2F5]+ cation features a symmetric [F2Br–μ-F–BrF2] bridge, whereas the [Brsub
Preparation of Two Quantum-Chemically Predicted, Isomeric [Br4F13]– Anions in the Solid State
Bandemehr, Jascha,Ivlev, Sergei I.,Karttunen, Antti J.,Kraus, Florian
, p. 4568 - 4576 (2020)
Two isomeric tridecafluoridotetrabromate(III) anions, [Br4F13]–, both previously predicted by quantum-chemical calculations, have serendipitously been obtained from the reaction of BrF3 with BaF2. Single crystals of Ba2[Br3F10]2[Br4F13]2 were selected from the reaction mixture at approximately 10 °C. The crystal structure contains two novel, isomeric [Br4F13]– anions besides the known, star-shaped [Br3F10]– anions. It crystallized in the monoclinic space group P1n1 (No. 7) with a = 8.8519(18), b = 15.217(3), c = 14.628(3) ?, β = 90.34(3)°, V = 1970.4(7) ?3 and Z = 2, mP124 at 100 K. The compound was additionally investigated using quantum-chemical solid-state calculations. If however crystals from the above reaction mixture were selected at room temperature, the compound Ba[Br3F10]2·BrF3 was obtained containing disordered BrF3 molecules of crystallization besides [Br3F10]– anions. The [Br4F13]– molecules were no longer present. Ba[Br3F10]2·BrF3 crystallized in the cubic space group Pa3 (No. 205) with a = 12.4903(14) ?, V = 1948.6(7) ?3, Z = 4, cP124, T = 100 K. The much easier to handle latter compound was additionally investigated using powder X-ray diffraction, as well as IR and Raman spectroscopy.
X-RAY INVESTIGATION OF THE STRUCTURE OF LIQUID BROMINE TRIFLUORIDE
Mit'kin, V. N.,Yur'ev, G. S.,Zemskov, S. V.,Kazakova, V. I.
, p. 60 - 67 (1987)
Using X-ray methods appropriate to liquids we determined the nearest neighbor coordination in liquid bromine trifluoride at 298 K.We have proposed a model for the structure which takes into account the presence of associated and nonassociated forms.
Enthalpy of sublimation of platinum tetrafluoride
Bondarenko, A. A.,Korobov, M. V.,Mitkin, V. N.,Sidorov, L. N.
, p. 299 - 304 (1988)
The saturated vapour of platinum tetrafluoride was studied by Knudsen-cell mass spectrometry.The only gaseous species found was PtF4(g).The molar sublimation enthalpy: ΔsubHm0(PtF4, 298.15 K) = (207 +/- 16)kJ.mol-1/s
Sorption and desorption of BrF3 on NaF: Studies on thermodynamics and kinetics
Zherin,Rudnikov,Ostvald,Sobolev,Amelina
supporting information, p. 25 - 33 (2019/03/27)
Temperature dependence of bromine trifluoride vapor pressure over its adduct with sodium fluoride has been determined; the adduct normal dissociation temperature has been determined. Kinetics of sorption and desorption processes in BrF3(gas)–NaF(solid) system have been studied. The equation was proposed to illustrate the link between forward reaction rate (Ка) described by Arrhenius equation and experimental value (Ki): Ki= Kа? (Pa/Peq)m, where Ki – observed reaction rate constant, Ka – forward reaction rate constant described by Arrhenius equation; Pa – partial pressure of BrF3; Peq – equilibrium pressure of BrF3 above BrF3?3NaF; m – factor characterizing the interaction area of BrF3 with NaF. The application of this equation makes possible to determine the true reaction rate values and reaction activation energy in chemisorption terms; it also helps to calculate the degree BrF3 sorption on NaF reaction at different temperatures and adsorbate pressures. The possibility of sorption-desorption separation of bromine trifluoride – uranium hexafluoride – iodine pentafluoride system with use of sodium fluoride was shown.
Synthesis of difluoroaryldioxoles using BrF3
Hagooly, Youlia,Welch, Michael J.,Rozen, Shlomo
, p. 902 - 905 (2011/03/22)
A novel synthesis of different aromatic and heteroaromatic difluorodioxole derivatives has been developed. The starting materials were catechols, which, after treatment with thiophosgene, formed at 0 °C the respective thiodioxoles. The latter were reacted for a short time with commercially available bromine trifluoride, producing potentially biologically important difluoroaryldioxoles in moderate to high yields.
Crystal structures of XeF5+MF4- (M = Ag, Au) and their relevance to the basicity and oxidizability of MF4-
Lutar, Karel,Jesih, Adolf,Leban, Ivan,Zemva, Boris,Bartlett, Neil
, p. 3467 - 3471 (2008/10/08)
XeF5+AuF4- has been prepared from BrF3·AuF3 by displacement of BrF3 with XeF6. The salt interacts quantitatively with KrF2 in anhydrous HF, below 0°C, to yield XeF5+AuF6-. XeF5AuF4 (I) is isostructural with XeF5AgF4 (II), and these compounds crystallize in space group I4/m with the following unit cell dimensions: I, ao = 5.735 (5) A?, co = 20.007 (17) A?, V = 658 (2) A?3, Z = 4; II, ao = 5.593 (2) A?, co = 20.379 (5) A?, V = 637.5 (8) A?3, Z = 4. The structure of II was solved by the Patterson method and refined to conventional R and Rw values of 0.077 and 0.090, respectively. The structure contains double layers of XeF5+ and layers of AgF4- ions, all layers being parallel to the ab plane. The XeF5+ ion had C4v symmetry with Xe-F(axial) = 1.853 (19) A?, Xe-F(equatorial) = 1.826 (9) A?, and F(axial)-Xe-F(equatorial) = 77.7 (3)°. The anion (site symmetry D2h), which is not significantly different from O4h symmetry, has Ag-F = 1.902 (11) A?. Differences between the XeF5AgF4 and XeF5AuF4 structures are attributed to lower ligand charges in the anion of the former, relative to those in the latter, and these in turn are related to observed differences in the basicity and oxidizability of the anions.
Reactivity of transition metal fluorides. III. Higher fluorides of vanadium, niobium, and tantalum
Canterford,O'Donnell
, p. 1442 - 1446 (2008/10/08)
A series of oxidation-reduction and halogen-exchange reactions has been used to compare the chemical reactivities of the pentafluorides of vanadium, niobium, and tantalum. Vanadium pentafluoride is extremely reactive and its reaction pattern with many reagents is extremely complex, depending largely on relative proportions of reagents and other experimental conditions. The pentafluorides of niobium and tantalum are very much less reactive than that of vanadium and are similar to each other. There is some evidence that of the two, the niobium compound is slightly more reactive. The reactivities of these three pentafluorides are discussed in terms of their physical properties and in relation to the higher fluorides of neighboring transition elements.