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7637-07-2Relevant articles and documents
Synthesis, thermal investigations and kinetic data of Zn(BF 4)2?6H2O
Nikolova, Deyanka,Georgiev
, p. 319 - 321 (2009)
The thermal dehydration and decomposition of Zn(BF4) 2?6H2O have been studied by TG, DTA and DSC analyses. It is found that the dehydration occurs in two steps. Following the experimental results a thermal decomposition sc
The chloryl cation, ClO2+
Christe, Karl O.,Schack, Carl J.,Pilipovich, Donald,Sawodny, Wolfgang
, p. 2489 - 2494 (1969)
The 1:1 adducts ClO2F·AsF5 and ClO2F·BF3 have been investigated. Whereas ClO2F·AsF5 is stable at ambient temperature, the ClO2F·BF3 adduct shows a dissociation pressure of 225 mm at 25°. A pressure-temperature curve gives a heat of reaction of 24.0 kcal mol-1, for the dissociation process: ClO2F·BF3(s) = ClO2F(g) + BF3(g). The X-ray powder patterns of ClO2F·AsF5 and ClF3·AsF5 were recorded and indexed. Infrared and Raman measurements show that ClO2F·AsF5 and ClO2F·BF3 have the ionic structures ClO2+AsF6- and ClO2+BF4-, respectively, in the solid state. All fundamental vibrations were observed and a valence force field was calculated for ClO2+.
Tetrachloro- and tetrabromoarsonium(v) cations: Raman and 75As, 19F NMR spectroscopic characterization and X-ray crystal structures of [AsCl4][As(OTeF5)6] and [AsBr4] [AsF(OTeF5)5]
Gerken, Michael,Kolb, Peter,Wegner, Andreas,Mercier, Helene P. A.,Borrmann, Horst,Dixon, David A.,Schrobilgen, Gary J.
, p. 2813 - 2824 (2000)
The salts [AsX4][As(OTeF5)6] and [AsBr4][AsF(OTeF5)5] (X = Cl, Br) have been prepared by oxidation of AsX3 with XOTeF5 in the presence of the OTeF5 acceptors As(OTeF5)5 and AsF(OTeF5)4. The mixed salts [AsCl4][Sb(OTeF5)(6-n)Cl(n-2)] and [ASCl4][Sb(OTeF5)(6-n)Cl(n)] (n ≥ 2) have also been prepared. The AsBr4+ cation has been fully structurally characterized for the first time in SO2ClF solution by 75As NMR spectroscopy and in the solid state by a single-crystal X-ray diffraction study of [AsBr4][AsF(OTeF5)5]: P1, a = 9.778(4) A, b = 17.731(7) A, c = 18.870(8) A, a = 103.53(4)°, β = 103.53(4)°, γ = 105.10(4)°, V = 2915(2) A3, Z = 4, and R1 = 0.0368 at -183 °C. The crystal structure determination and solution 75As NMR study of the related [AsCl4]-[As(OTeF5)6] salt have also been carried out: [AsCl4][As(OTeF5)6], R3, a = 9.8741(14) A, c = 55.301(11) A, V = 4669(1) A3, Z = 6, and R1 = 0.0438 at -123 °C; and R3, a = 19.688(3) A, c = 55.264(11) A, V = 18552(5) A3, Z = 24, and R1 = 0.1341 at -183 °C. The crystal structure of the As(OTeF5)6- salt reveals weaker interactions between the anion and cation than in the previously known AsF6- salt. The AsF(OTeF5)5- anion is reported for the first time and is also weakly coordinating with respect to the AsBr4+ cation. Both cations are undistorted tetrahedra with bond lengths of 2.041 (5)-2.056(3) A for AsCl4+ and 2.225(2)-2.236(2) A for AsBr4+. The Raman spectra are consistent with undistorted AsX4+ tetrahedra and have been assigned under T(d) point symmetry. The 35Cl/37Cl isotope shifts have been observed and assigned for AsCl4+, and the geometrical parameters and vibrational frequencies of all known and presently unknown PnX4+ (Pn = P, As, Sb, Bi; X = F, Cl, Br, I) cations have been calculated using density functional theory methods.
Preparation and properties of perfluoroammonium tetrafluoroborate, NF4+BF4-, and possible synthesis of nitrogen pentafluoride
Goetschel,Campanile,Curtis,Loos,Wagner,Wilson
, p. 1696 - 1701 (1972)
A new crystalline compound, NF4+BF4-, has been prepared by exposing the heterogeneous ternary system NF3-BF3-F2 to 3-MeV bremsstrahlung at 77°K. The G value for the reaction (molecules isolated per 100 eV absorbed) is about unity. The compound is stable at room temperature in dry air; it decomposes above 250° to the reactants. It reacts rapidly with moisture and with organic substances. The indicated ionic structure is confirmed by infrared and Raman spectroscopy. The X-ray powder pattern can be indexed on the basis of a tetragonal unit cell with a = 7.01 and c = 5.22 A?. Irradiation of mixtures of nitrogen trifluoride and excess fluorine at 77°K has led to isolation in low yields of a white solid. It decomposes below 143°K to liberate nitrogen trifluoride and reacts with boron trifluoride at low temperature to form NF4BF4. Its most likely identity is perfluoroammonium fluoride.
Li2B6O9F2, a new acentric fluorooxoborate
Pilz, Thomas,Jansen, Martin
, p. 2148 - 2152 (2011)
Novel Li2B6O9F2 can be either synthesized from LiBF4 and B2O3 or from LiB3O5 and LiBF4, at 673 K. The three dimensional anionic network is related to the polymeric anion of pentaborates MB5O8 (M: Rb, Cs); replacing one bridging oxygen atom per repetition unit of the latter by BF2O2 tetrahedron yields the again three dimensional fluorooxoborate anion of the title compound.The new solid electrolyte is stable up to 753 K and decomposes evolving BF3. It is a purely ionic conductor with conductivities of 1.3 × 10 -8 and 2.2 A- 10-10S·cm-1 at 573 and 473 K, respectively. Copyright
Mechanism of the benzenediazonium tetrafluoroborate thermolysis in the solid state
Koval'chuk, Eugen P.,Reshetnyak, Oleksandr V.,Kozlovs'ka, Zoryana Ye.,B?azejowski, Jerzy,Gladyshevs'kyj, Roman Ye.,Obushak, Mykola D.
, p. 1 - 5 (2006)
The thermolysis of benzenediazonium tetrafluoroborate was studied by thermogravimetry in dynamic mode. The decomposition of [ArN{triple bond, long}N]+BF4- in the solid state with the formation of C6H5F, BF3, C6H6, and N2 starts at T > 348 K. The speed of the thermolysis was estimated gravimetrically and by infrared spectroscopy, considering the change of the intensity of the absorption band at 1498 cm-1, which corresponds to fluorobenzene. The maximal rate of thermolysis observes at the 366.5 K. A kinetic scheme, which includes the formation of a neutral complex [C6H5δ+?BF4 δ-], is proposed for the thermolysis of arenediazonium tetrafluoroborate. The decomposition of the complex with the formation of free-radical intermediates explains the chain character of the thermolysis.
Nucleophilicity of Alkyl Zirconocene and Titanocene Precatalysts, and Kinetics of Activation by Carbenium Ions and by B(C6F5)3
Berionni, Guillaume,Kurouchi, Hiroaki,Eisenburger, Lucien,Mayr, Herbert
supporting information, p. 11196 - 11200 (2016/08/03)
Kinetics of activation of methyl and benzyl metallocene precatalysts by benzhydrylium ions, tritylium ions, and triarylborane B(C6F5)3were measured spectrophotometrically. The rate constants correlate linearly with the electrophilicity parameter E of the benzhydrylium and tritylium ions employed, allowing us to determine the σ-nucleophilicities of the metal–carbon bond of several zirconocenes and titanocenes. Bridging, substitution, metal, and ligand effects on the rates of metal–alkyl bond cleavage (M=Zr, Ti) were studied and structure–reactivity correlations were used to predict the kinetics of generation of metallocenium ions pairs, which are active catalysts in polymerization reactions and are highly electrophilic Lewis acids in frustrated Lewis pair catalysis.
Xenon(IV)-carbon bond of [C6F5XeF2]+; Structural characterization and bonding of [C6F5XeF2][BF4], [C6F5XeF2][BF4]·2HF, and [C6F5XeF2][BF4]· n NCCH 3 (n = 1, 2); And the fluorinating properties of [C6F5XeF2][BF4]
Koppe, Karsten,Haner, Jamie,Mercier, Hlne P. A.,Frohn, Hermann-J.,Schrobilgen, Gary J.
, p. 11640 - 11661 (2015/01/16)
The [C6F5XeF2]+ cation is the only example of a XeIV-C bond, which had only been previously characterized as its [BF4]- salt in solution by multi-NMR spectroscopy. The [BF4]- salt and its new CH3CN and HF solvates, [C6F5XeF2][BF4]·1.5CH3CN and [C6F5XeF2][BF4]·2HF, have now been synthesized and fully characterized in the solid state by lowerature, single-crystal X-ray diffraction and Raman spectroscopy. Crystalline [C6F5XeF2][BF4] and [C6F5XeF2][BF4]·1.5CH3CN were obtained from CH3CN/CH2Cl2 solvent mixtures, and [C6F5XeF2][BF4]·2HF was obtained from anhydrous HF (aHF), where [C6F5XeF2][BF4]·1.5CH3CN is comprised of an equimolar mixture of [C6F5XeF2][BF4]·CH3CN and [C6F5XeF2][BF4]·2CH3CN. The crystal structures show that the [C6F5XeF2]+ cation has two short contacts with the F atoms of [BF4]- or with the F or N atoms of the solvent molecules, HF and CH3CN. The lowerature solid-state Raman spectra of [C6F5XeF2][BF4] and C6F5IF2 were assigned with the aid of quantum-chemical calculations. The bonding in [C6F5XeF2]+, C6F5IF2, [C6F5XeF2][BF4], [C6F5XeF2][BF4]·CH3CN, [C6F5XeF2][BF4]·2CH3CN, and [C6F5XeF2][BF4]·2HF was assessed with the aid of natural bond orbital analyses and molecular orbital calculations. The 129Xe, 19F, and 11B NMR spectra of [C6F5XeF2][BF4] in aHF are reported and compared with the 19F NMR spectrum of C6F5IF2, and all previously unreported J(129Xe-19F) and J(19F-19F) couplings were determined. The long-term solution stabilities of [C6F5XeF2][BF4] were investigated by 19F NMR spectroscopy and the oxidative fluorinating properties of [C6F5XeF2][BF4] were demonstrated by studies of its reactivity with K[C6F5BF3], Pn(C6F5)3 (Pn = P, As, or Bi), and C6F5X (X = Br or I).
Quantum-chemical calculations and IR spectra of the (F2)MF 2 molecules (M = B, Al, Ga, In, Tl) in solid matrices: A new class of very high electron affinity neutral molecules
Wang, Xuefeng,Andrews, Lester
, p. 3768 - 3771 (2011/04/26)
Electron-deficient group 13 metals react with F2 to give the compounds MF2 (M = B, Al, Ga, In, Tl), which combine with F 2 to form a new class of very high electron affinity neutral molecules, (F2)MF2, in solid argon and neon. These (F 2)MF2 fluorine metal difluoride molecules were identified through matrix IR spectra containing new antisymmetric and symmetric M-F stretching modes. The assignments were confirmed through close comparisons with frequency calculations using DFT methods, which were calibrated against the MF3 molecules observed in all of the spectra. Electron affinities calculated at the CCSD(T) level fall between 7.0 and 7.8 eV, which are in the range of the highest known electron affinities.
GASEOUS DIELECTRICS WITH LOW GLOBAL WARMING POTENTIALS
-
, (2010/12/31)
A dielectric gaseous compound which exhibits the following properties: a boiling point in the range between about ?20° C. to about ?273° C.; non-ozone depleting; a GWP less than about 22,200; chemical stability, as measured by a negative standard enthalpy of formation (dHf0); a toxicity level such that when the dielectric gas leaks, the effective diluted concentration does not exceed its PEL; and a dielectric strength greater than air.