cas 7637-07-2, Boron trifluoride | Articles data

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Synthesis, thermal investigations and kinetic data of Zn(BF 4)2?6H2O
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
Nikolova, Deyanka,Georgiev
p. 319 - 321
(2009)
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The chloryl cation, ClO2+
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+.
Christe, Karl O.,Schack, Carl J.,Pilipovich, Donald,Sawodny, Wolfgang
p. 2489 - 2494
(1969)
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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]
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.
Gerken, Michael,Kolb, Peter,Wegner, Andreas,Mercier, Helene P. A.,Borrmann, Horst,Dixon, David A.,Schrobilgen, Gary J.
p. 2813 - 2824
(2000)
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Preparation and properties of perfluoroammonium tetrafluoroborate, NF4+BF4-, and possible synthesis of nitrogen pentafluoride
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.
Goetschel,Campanile,Curtis,Loos,Wagner,Wilson
p. 1696 - 1701
(1972)
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Li2B6O9F2, a new acentric fluorooxoborate
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
Pilz, Thomas,Jansen, Martin
p. 2148 - 2152
(2011)
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Mechanism of the benzenediazonium tetrafluoroborate thermolysis in the solid state
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.
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)
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Nucleophilicity of Alkyl Zirconocene and Titanocene Precatalysts, and Kinetics of Activation by Carbenium Ions and by B(C6F5)3
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.
Berionni, Guillaume,Kurouchi, Hiroaki,Eisenburger, Lucien,Mayr, Herbert
supporting information
p. 11196 - 11200
(2016/08/03)

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]
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).
Koppe, Karsten,Haner, Jamie,Mercier, Hlne P. A.,Frohn, Hermann-J.,Schrobilgen, Gary J.
p. 11640 - 11661
(2015/01/16)

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
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.
Wang, Xuefeng,Andrews, Lester
p. 3768 - 3771
(2011/04/26)

GASEOUS DIELECTRICS WITH LOW GLOBAL WARMING POTENTIALS
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.
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(2010/12/31)

OXONIUM AND SULFONIUM SALTS
The present invention relates to oxonium salts having [(Ro)3O]+ cations and sulfonium salts having [(Ro)3S]+ cations, where Ro denotes straight-chain or branched alkyl groups having 1-8 C atoms or phenyl which is unsubstituted or substituted by Ro, ORo, N(Ro)2, CN or halogen, and anions selected from the group of [PFx(CyF2y+1?zHz)6?x]? anions, where 2≦x≦5, 1≦y≦8 and 0≦z≦2y+1, or anions selected from the group of [BFn(CN)4?n]? anions, where n=0, 1 , 2 or 3, or anions selected from the group of [(Rf1SO2)2N]? anions or anions selected from the group of [BFwRf24?w]? anions, to processes for the preparation thereof, and to the use thereof, in particular for the preparation of ionic liquids.
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Page/Page column 10

(2009/03/07)

Development and implementation of industrial technologies for synthesis of fluorine compound with the application of elemental fluorine
A survey is given on the application of elemental fluorine in chemical plants and research centers of Russian Federation.
Pashkevich,Barabanov,Maksimov
p. 1142 - 1148
(2009/12/01)

High gas storage capacities for ionic liquids through chemical complexation
Gases with sufficient Lewis acidity or basicity form weak and reversible complexes with carefully selected ionic liquids. We have prepared ionic liquid complexes with PH3 and BF3 that provide large gas capacities in the liquid phase
Tempel, Daniel J.,Henderson, Philip B.,Brzozowski, Jeffrey R.,Pearlstein, Ronald M.,Cheng, Hansong
p. 400 - 401
(2008/09/19)

Vibrational overtone spectrum of matrix isolated cis, cis-HOONO
Cis, cis-peroxynitrous acid is known to be an intermediate in atmospheric reactions between OH and N O2 as well as HOO and NO. The infrared absorption spectra of matrix-isolated cc-HOONO and cc-DOONO in argon have been observed in the range of 500-8000 cm-1. Besides the seven fundamentalvibrational modes that have been assigned earlier for this molecule [Zh ang, J. Chem. Phys. 124, 084305 (2006)], more than 50 of the overtone and combination bands have been observed for cc-HOONO and cc-DOONO. Ab initio CCSD(T)/atomic natural orbital anharmonic force field calculations were used to help guide the assignments. Based on this study of the vibrational overtone transitions of cis, cis-HOONO that go as high as 8000 cm-1 and the earlier paper on the vibrational fundamentals, we conclude that the CCSD(T)/ANO anharmonic frequencies seem to correct to ±35 cm-1. The success of the theoretically predicted anharmonic frequencies {} in assigning overtone spectra of HOONO up to 8000 cm-1 suggests that the CCSD(T)/ANO method is producing a reliable potential energy surface for this reactive molecule.
Zhang, Xu,Nimlos, Mark R.,Ellison, G. Barney,Varner, Mychel E.,Stanton, John F.
p. 1 - 5
(2009/02/03)

Reaction of corundum with a molten mixture of potassium and sodium tetrafluoroborates
Dissolution of synthetic corundum in KBF4-NaBF4 melts was studied as influenced by the composition of the salt mixture and temperature. The optimal parameters of the process for removal of synthetic corundum rods from internal channels of castings were determined.
Zarubitskii,Dmitruk
p. 1048 - 1051
(2008/02/04)

Homoleptic, σ-bonded octahedral superelectrophilic metal carbonyl cations of iron(II), ruthenium(II), and osmium(II). Part 2: Syntheses and characterizations of [M(CO)6][BF4]2 (M = Fe, Ru, Os)
As the first examples of homoleptic, σ-bonded superelectrophilic metal carbonyl cations with tetrafluoroborate [BF4]- as the counter anions three thermally stable salts of the composition [M(CO) 6[BF4]2 (M = Fe, Ru, Os) have been synthesized and extensively characterized by thermochemical, structural, and spectroscopic methods. A common synthetic route, the oxidative carbonylation of either Fe(CO)5 (XeF2 as the oxidizer) or M3(CO) 12 (M = Ru, Os) (F2 as the oxidizer) in the conjugate Bronsted-Lewis superacid HF/BF3, was employed. The thermal behavior of the three salts, studied by differential scanning calorimetry (DSC) and gas-phase IR spectroscopy of the decomposition products, has been compared to that of the corresponding [SbF6]- salts. The molecular structures of [M(CO)6]-[BF4]2 (M = Fe, Os) were obtained by single-crystal X-ray diffraction at 100 K. X-ray powder diffraction data for [M(CO)6][BF4]2 (M = Ru, Os) were obtained between 100 and 300 K in intervals of 50 K. All three salts are isostructural and crystallized in the tetragonal space group /4/m (No. 87). As for the corresponding [M(CO)6][SbF6]2 salts (M = Fe, Ru, Os), similar unit cell parameters and vibrational fundamentals were also found for the three [BF4]- compounds. For the structurally characterized salts [M(CO)6][BF4] 2 (M = Fe, Os), very similar bond parameters for both cations and anions were found. Hence, the invariance of structural and spectroscopic properties of [M(CO)6]2+ cations (M = Fe, Ru, Os) extended from the fluoroantimonates [Sb2F11]- and [SbF6]- as counteranions also to [BF4] -.
Finze, Maik,Bernhardt, Eduard,Willner, Helge,Lehmann, Christian W.,Aubke, Friedhelm
p. 4206 - 4214
(2008/10/09)

Rearrangement Reactions of the Transient Lewis Acids (CF3) 3B and (CF3)3BCF2: An Experimental and Theoretical Study
Short-lived (CF3)3B and (CF3) 3BCF2 are generated as intermediates by thermal dissociation of (CF3)3BCO and F-abstraction from the weak coordinating anion [B(CF3)4]-, respectively. Both Lewis acids cannot be detected because of their instability with respect to rearrangement reactions at the B-C-F moiety. A cascade of 1,2-fluorine shifts to boron followed by perfluoroalkyl group migrations and also difluorocarbene transfer reactions occur. In the gas phase, (CF 3)3B rearranges to a mixture of linear perfluoroalkyldifluoroboranes CnF2n+1BF2 (n = 2-7), while the respective reactions of (CF3)3BCF 2 result in a mixture of linear (n = 2-4) and branched monoperfluoroalkyldifluoroboranes, e.g., (C2F5)(CF 3)FCBF2. For comparison, the reactions of [CF 3BF3]- and [C2F5BF 3]- with AsF5 are studied, and the products in the case of [CF3BF3]- are BF3 and C2F5BF2 whereas in the case of [C 2F5BF3]-, C2F 5BF2 is the sole product. In contrast to reports in the literature, it is found that CF3BF2 is too unstable at room temperature to be detected. The decomposition of (CF3) 3BCO in anhydrous HF leads to a mixture of the new conjugate Bronsted-Lewis acids [H2F][(CF3)3BF] and [H2F][C2F5BF3]. All reactions are modeled by density functional calculations. The energy barriers of the transition states are low in agreement with the experimental results that (CF3)3B and (CF3)3BCF2 are short-lived intermediates. Since CF2 complexes are key intermediates in the rearrangement reactions of (CF3)3B and (CF3)3BCF2, CF2 affinities of some perfluoroalkylfluoroboranes are presented. CF2 affinities are compared to CO and F- affinities of selected boranes showing a trend in Lewis acidity, and its influence on the stability of the complexes is discussed. Fluoride ion affinities are calculated for a variety of different fluoroboranes, including perfluorocarboranes, and compared to those of the title compounds.
Finze, Maik,Bernhardt, Eduard,Zaehres, Manfred,Willner, Helge
p. 490 - 505
(2008/10/09)

Silver(I) Undecafluorodiantimonate(V)
The reaction between AgBF4 and excess of SbF5 in anhydrous hydrogen fluoride (aHF) yields the white solid AgSb2F 11 after the solvent and the excess of SbF5 have been pumped off. Reaction between equimolar amounts of AgSb2F 11 and AgBF4 yields AgSbF6. Meanwhile, oxidation of solvolyzed AgSb2F11 in aHF by elemental fluorine yields a clear blue solution of solvated Ag(II) cations and SbF 6- anions. AgSb2F11 is orthorhombic, at 250 K, Pbca, with a = 1091.80(7) pm, b = 1246.28(8) pm, c = 3880.2(3) pm, V = 5.2797(6) nm3, and Z = 24. The crystal structure of AgSb2F 11 is related to the already known crystal structure of H 3OSb2F11. Vibrational spectra of AgSb 2F11 entirely match the literature-reported vibrational spectra of β-Ag(SbF6)2, for which a formulation of a mixed-valence Ag(I)/Ag(III) compound was suggested (AgIAg III(SbF6)4). On the basis of obtained results it can be concluded that previously reported β-Ag(SbF6) 2 is in fact Ag(I) compound with composition AgSb2F 11.
Mazej, Zoran,Benkic, Primoz
p. 8337 - 8343
(2008/10/09)

Preparation of 1-X-2,2-Difluoroethenylxenon(II) Tetrafluoroborates [CF 2=CXXe][BF4]
The new type of alkenylxenon(II) salts [CF2=CXXe] [BF 4] (X = H, Cl, CF3) was prepared by reacting the corresponding alkenyldifluoroboranes CF2=CXBF2 with XeF2 in 1,1,1,3,3-pentafluoropropa
Frohn, Hermann-Josef,Bardin, Vadim V.
p. 2465 - 2469
(2008/10/09)

The Reaction of 2-X-1,2-Difluoroalk-1-enyldifluoroboranes with Xenon Difluoride. A Methodical Approach to 1,2-Difluoroalk-1-enylxenon(II) Salts
2-X-1,2-Difluoroalk-1-enylxenon(II) salts were prepared by the reaction of XeF2 with XCF=CFBF2 (X = F, trans-H, cis-Cl, trans-Cl, cis-CF3, cis-C2F5) but no organoxenon(II) compounds were obtained when the trans-isomers of boranes, trans-XCF=CFBF 2 (X = CF3, C4F9, C 4H9, Et3Si), were used under similar conditions.
Frohn, Hermann-Josef,Adonin, Nicolay Yu.,Bardin, Vadim V.
p. 2499 - 2508
(2008/10/09)

Studies on BCl and on the exchange reaction of BCl3 with polyboron flourides
Gaseous BCl has been prepared at low pressure by reaction of BCl3 with boron at 2000 °C or by decomposition of B2Cl4 using either an electric discharge or using flash thermolysis at 1150 °C, and then condensed at - 196 °C. Reasons are discussed why each method gives BCl capable of generating (Cl2B)3BCO when the condensate at - 196 °C is treated with CO, but B4Cl4 is only formed from BCl prepared from B2Cl4. The stepwise conversion of (F2B)3BCO to (Cl2B)3BCO by treatment with BCl3 has been followed by 11B NMR spectroscopy. Evidence from mass spectrometry and 11B NMR spectroscopy suggests that reaction of polyboron fluorides, particularly B8F12 and B10F12, with BCl3 yields a new form of B9Cl9 of, as yet, unknown structure which converts slowly to closo-B9Cl9 or closo-B8Cl8 depending on the solvent.
Pardoe, Jennifer A.J.,Norman, Nicholas C.,Timms, Peter L.
p. 543 - 548
(2008/10/08)

Tris(trifluoromethyl)borane carbonyl, (CF3)3BCO - Synthesis, physical, chemical and spectroscopic properties, gas phase, and solid state structure
Tris(trifluoromethyl)borane carbonyl, (CF3)3BCO, is obtained in high yield by the solvolysis of K[B(CF3)4] in concentrated sulfuric acid. The in situ hydrolysis of a single bonded CF3 group is found to be a simple, unprecedented route to a new borane carbonyl. The related, thermally unstable borane carbonyl, (C6F5)3BCO, is synthesized for comparison purposes by the isolation of (C6F5)3B in a matrix of solid CO at 16 K and subsequent evaporation of excess CO at 40 K. The colorless liquid and vapor of (CF3)3BCO decomposes slowly at room temperature. In the gas phase t1/2 is found to be 45 min. In the presence of a large excess of 13CO, the carbonyl substituent at boron undergoes exchange, which follows a first-order rate law. Its temperature dependence yields an activation energy (EA) of 112 kJ mol-1. Low-pressure flash thermolysis of (CF3)3BCO with subsequent isolation of the products in iow low-temperature matrixes, indicates a lower thermal stability of the (CF3)3B fragment, than is found for (CF3)3BCO. Toward nucleophiles (CF3)3-BCO reacts in two different ways: Depending on the nucleophilicity of the reagent and the stability of the adducts formed, nucleophilic substitution of CO or nucleophilic addition to the C atom of the carbonyl group are observed. A number of examples for both reaction types are presented in an overview. The molecular structure of (CF3)3BCO in the gas phase is obtained by a combined microwave-electron diffraction analysis and in the solid state by single-crystal X-ray diffraction. The molecule possesses C3 symmetry, since the three CF3 groups are rotated off the two possible positions required for C3v symmetry. All bond parameters, determined in the gas phase or in the solid state, are within their standard deviations in fair agreement, except for internuclear distances most noticeably the B-CO bond lengths, which is 1.69(2) A in the solid state and 1.617(12) A in the gas phase. A corresponding shift of v(CO) from 2267 cm-1 in the solid state to 2251 cm-1 in the gas phase is noted in the vibrational spectra. The structural and vibrational study is supported by DFT calculations, which provide, in addition to the equilibrium structure, confirmation of experimental vibrational wavenumbers, IR-band intensities, atomic charge distribution, the dipole moment, the B-CO bond energy, and energies for the elimination of CF2 from (CF3)xBF3-x, x = 1-3. In the vibrational analysis 21 of the expected 26 fundamentals are observed experimentally. The 11B-, 13C-, and 19F-NMR data, as well as the structural parameters of (CF3)3BCO, are compared with those of related compounds.
Finze, Maik,Bernhardt, Eduard,Terheiden, Annegret,Berkei, Michael,Willner, Helge,Christen, Dines,Oberhammer, Heinz,Aubke, Friedhelm
p. 15385 - 15398
(2007/10/03)

Phase transition and thermal decomposition of [Cd(H2O)6](BF4)2
Phase transition and thermal decomposition of [Cd(H2O)6](BF4)2 were studied by differential scanning calorimetry (DSC), differential thermal analysis (DTA) and thermogravimetry (TG) methods. The solid-solid phas
Mikuli,Migdal-Mikuli,Gajerski
p. 861 - 864
(2008/10/08)

Introduction of ClO4-, NO3-, and C(NO2)3- anions into the coordination sphere of boron by directly reacting salts with boron halides
We established that salts of ClO4-, NO 3-, and C(NO2)3- anions (Y) directly react with boron halides BX3 (X = F, Cl, Br) to yield [X3BA]- complex anions. The [X3BOClO 3]- (X = F, Cl, Br) anions are stable in a CHCl 3 solution. They are isolated as salts of R4N+ cations in the solid state. Their IR and 11B NMR spectra are characterized. The decomposition of R4N[X3BOClO 3] salts starts with the elimination of part of the boron halide and ends by the irreversible decomposition of a solid residue at above 200°C. The enthalpies of dissociation of chloroperchloratoborates R 4N[Cl3BOClO3](cr) - R 4NClO4(cr) + BCl3(gas) are naturally positioned between the enthalpies of dissociation for salts of BCl4- and [B(C1O4)4]-. The donating bond energy of ClO4- to a boron atom is similar to the energy of an ordinary chemical bond. The BCl3 reactions with nitrates and nitroform salts yield low-stability anions [Cl3BONO2] - and [Cl3BC(NO2)3]-. These anions are decomposed directly in the reaction medium (CHCl3). The initial stage is a disproportionation reaction to yield the end-members of the anion series: BCl4- and BF4-. (C2H5)4N[B(NO3)4] was isolated and identified in the reaction of BCl3 with (C 2H5)4N[B(NO3)4]. The possibility of {B[C(NO2)3]4}- formation was proven by counter synthesis: the complex salt (CH 3)4N{B[C(NO2)3]4 was prepared by reacting (CH3)4NBCl4 with excess AgC(NO2)3 at -50°C. The compound is unstable; it decomposes at -30°C with vigorous gas evolution.
Titova
p. 1121 - 1129
(2008/10/08)

Facile and mild deboronation of o-carboranes using cesium fluoride
The o-carborane and substituted derivatives were degrated effectively using cesium fluoride in ethanol under reflux conditions, producing cesium salts of nido monoanions directly in high yield.
Yoo,Hwang,Do
p. 568 - 570
(2008/10/08)

Method for producing and purifying 3-(3-hydroxyphenyl)-1,1,3-trimethylindan-5-ol
A process is disclosed for the preparation and purification of 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol. Accordingly, isopropenylphenol, its dimers or oligomers undergo isomerization in the presence of an acid catalyst, the reaction mixture is optionally neutralized by adding a base and 3-(4-hydroxyphenyl)-1,1,3-trimethylindan-5-ol is isolated by recrystallization.
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(2008/06/13)

(Fluoroorgano)fluoroboranes and -fluoroborates: Part 3. Polyfluoroalken-1-yldifluoroboranes
Polyfluoroalken-1-yldifluoroboranes RCF=CFBF2 (R=F, cis-, trans-Cl, trans-C4F9, cis-C2F5, cis-C6F13, trans-C4H9, trans-C6H5) were prep
Frohn,Bardin
p. 54 - 58
(2007/10/03)

Derivatives of bicyclo[2.2.1]heptane, method for their production, and traction fluid
Derivatives of bicyclo[2.2.1]heptane in the invention have a high traction coefficient under high temperature and an excellent viscosity characteristic under low temperature and are useful for the fluid for a traction drive, and a method in the invention produces such derivatives economically and efficiently.
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(2008/06/13)

Novel trityl activators with new weakly coordinating anions derived from C6F41,2-[B(C6F5)2] 2: Synthesis, strussctures, and olefin polymerization behavior
The weakly coordinating onions {C6F4-1,2-[B(C6F5)2] 2(μ-OR)}- (R = CH3, C6F5) were prepared as their trityl salts (2-OR) and fully characterized.
Clifford Williams,Irvine, Geoffry J.,Piers, Warren E.,Li, Zengmin,Collins, Scott,Clegg, William,Elsegood, Mark R. J.,Marder, Todd B.
p. 1619 - 1621
(2008/10/08)

Preparation of 3-methytetra-hydrofuran from 2,3-dihydrofuran
Disclosed is a two-step process wherein (1) 2,3-dihydrofuran is reacted with a trialkyl orthoformate in the presence of an acidic catalyst to produce a 2-alkoxy-3-(dialkoxymethyl)tetrahydrofuran intermediate and (2) the intermediate is contacted with hydrogen in the presence of a catalyst system comprising a Group VIII noble metal or rhenium and a strong acid to convert the intermediate to a mixture of 3-methyltetrahydrofuran (3-MeTHF) and 3-(hydroxymethyl)tetrahydrofuran (3-HOMeTHF). The 3-MeTHF produced in accordance with the present invention is useful as an industrial solvent and as a co-monomer in the manufacture of polymers such as elastomers. 3-HOMeTHF may be used as a solvent and in the manufacture of pharmaceutical and agricultural chemicals and acrylate and methacrylate esters for use in preparing polymers such as polyacrylates.
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(2008/06/13)

Classical and nonclassical nitrosyl hydride complexes of rhenium in various oxidation states
The paramagnetic rhenium complex [NEt4]2[Re(Br)5(NO)] (1) has been used to prepare a series of novel mononitrosyl hydride and dihydrogen rhenium complexes: [Re(Br)2(NO)(η2-H2)(PR3) 2] (R = iPr, 2a; Cy, 2b) and [Re(H)(BH4)(NO)(PR3)2] (R = iPr, 3a; Cy, 3b). The coordinated BH3 of the derivatives 3 can be replaced by the H2 or the NO ligand, thus leading to the tetrahydride and dinitrosyl species [Re(H)4(NO)L2] (R = iPr, 4a; Cy, 4b) or [Re(H)(NO)2(PR3)2] (R = iPr, 5a; Cy, 5b). While [Re(H)4(NO)(PPh3)2] does not seem to be stable, [Re(H)(NO)2(PPh3)2] (5c) has been obtained in a fashion similar to the preparation of 3a,b from the reaction of [Re(H)(BH4)(NO)(PPh3)2] and NOBF4. Detailed investigations of the reactions of 3a,b with NOBF4 have revealed that the compounds initially formed are the isolable BF3 adducts [Re(H)(NO)(NOBF3)(PR3)2] (R = iPr, 6a; Cy, 6b). The source of BF3 is the nitrosonium salt. Dissociation of BF3 from 6a,b takes place in donor solvents such as THF, affording the BF3-free compounds 5a,b, whereas in noncoordinating solvents such as toluene, benzene, or CH2Cl2 only the species 6a,b are observable. Apparently due to an unfavorable position of the dissociation equilibrium, the existence of the complex [Re(H)(NO)(NOBF3)(PPh3)2] could only be made plausible from dynamic NMR spectroscopic observations. Attempts to isolate it failed even from nonpolar solvents. X-ray diffraction studies have been carried out on the complexes [Re(Br)2(NO)(η2-H2)(PiPr 3)2] (2a), [Re(H)(BH4)(NO)(PR3)2] (R = iPr, 3a; Ph, 3c), [Re(H)(NO)2(PiPr3)2] (5a), and [Re(H)(NO)(NOBF3)(PiPr3)2] (6a). The hydrogen atoms of the η2-H2 moiety of 2a could not be located in the X-ray diffraction study, but their most probable position in the molecule has been traced by an extensive search based on DFT calculations.
Gusev, Dimitri,Llamazares, Angela,Artus, Georg,Jacobsen, Heiko,Berke, Heinz
p. 75 - 89
(2008/10/08)

Controlled formation of olefin oligomers
An oligomer is made by contacting a straight-chain, α-olefinic monomer with boron trifluoride and a hydroxy carbonyl promoter. The hydroxy carbonyl is preferably a β-hydroxy-ketone, such as 4-hydroxy-4-methyl-2-pentanone. A second promoter can be used in conjunction with the boron trifluoride and the hydroxy carbonyl promoter. Possible secondary promoters include aldehydes, alcohols, alcohol alkoxylates, carboxylic acids, ethers, ketones, and their mixtures. Preferably the oligomer product has a kinematic viscosity at 100° C. of less than 1.7 cSt; has a dimer to trimer and higher oligomer ratio of at least 1:1; and is at least 90 wt. % dimer and trimer of the monomer.
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(2008/06/13)

Synthesis of the cationic silyleneiron complex [(η-C5H5)Fe(CO)2=SiMe{2-(Me 2NCH2)C6H4}]PF6 by hydride abstraction from a (hydrosilyl)iron complex with Ph3CPF6
A cationic intramolecular base-stabilized silyleneiron complex, [(η-C5H5)Fe(CO)2=SiMe{2-(Me 2-NCH2)C6H4}]PF6, was synthesized by hydride abstraction from the (hydrosilyl)iron complex (η-C5H5)Fe-(CO)2SiHMe{2-(Me 2NCH2)C6H4} with Ph3CPF6. Reaction of the silylene complex with MeOH afforded the methoxysilyl complex [(η-C5H5)Fe(CO)2SiMeOMe{2-(Me 2N(H)CH2)C6H4}]PF6 in good yield. The molecular structures of the silylene and methoxysilyl complexes were determined by X-ray crystal structure analysis.
Kobayashi, Hideki,Ueno, Keiji,Ogino, Hiroshi
p. 5490 - 5492
(2008/10/09)

Process for producing aromatic acylation product
A process for producing an aromatic acylation product from an aromatic compound, an olefin and carbon monoxide, which comprises the steps of: (a) reacting an olefin with carbon monoxide in the presence of hydrogen fluoride and boron trifluoride at a pressure of not more than 100 kg/cm2 G to prepare an acyl fluoride synthesis solution, (b) allowing the acyl fluoride synthesis solution to absorb boron trifluoride to form a complex of acyl fluoride and boron trifluoride, (c) subjecting an aromatic compound to an acylation reaction with a reaction mixture containing the complex of acyl fluoride and boron trifluoride, obtained in the step (b), to form a complex of boron trifluoride, hydrogen fluoride and an aromatic acylation compound, provided that the amount of the acyl fluoride in the complex of acyl fluoride and boron trifluoride is less than 1 mole per mole of the aromatic compound, and (d) separating the aromatic acylation compound from the complex formed in the step (c) by heating a reaction mixture obtained in the step (c).
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(2008/06/13)

Bis-(indolyl)ethylenes
Bis-(indolyl)ethylenes of the following general formula are prepared: STR1 wherein a is 1 or 2, wherein b is 1 or 2, wherein each A is independently selected from a dialkylamino, dialkoxyalkylamino, diaroxyalkylamino, diarylamino, alkylarylamino, dicyloalkylamino, alkylcycloalkylamino, arylcycloalkylamino, pyrrolidino, piperidino, or morpholino radical, wherein each B is independently selected from A or an alkoxy, alkoxyalkyl or aroxy radical, wherein each R is independently selected from hydrogen, halogen, alkyl, or alkoxy, wherein each of R5, R5', R6, and R6' are each independently selected from hydrogen, alkyl (C1 -C8), alkoxyalkyl, aroxyalkyl, halogen, phenyl, or phenyl substituted by alkyl or alkoxy, the alkyl moieties referred to herein being of one to eight carbons, the cycloalkyl moieties referred to herein being of three to six carbons.
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(2008/06/13)

Bis-(indolyl)ethylenes
Novel bis-(indolyl)ethylenes, process for their production and record systems utilizing such bis-(indolyl)ethylene chromogens are described. Bis-(indolyl)ethylenes of the following general formula are prepared: STR1 wherein each L1 and L2 is the same or different and is each independently selected from indole moieties (J1) through (J4) (L1 need not be the same as L2), STR2 wherein in (J1) through (J4) above, each of R5, R6, R13, R14, R21, R22, R29 and R30 need not be the same and is each independently selected from hydrogen, alkyl (C1 -C8), cycloalkyl, alkylaroxy, alkylalkoxy, and substituted or unsubstituted aryl, such as phenyl, naphthyl, or heterocyclyl. Each of R1, R2, R3, R4, R7, R8, R9, R10, R11, R12, R15, R16, R17, R18, R19, R20, R23, R24, R25, Rphu 26, R27, and R28 need not be the same and is each independently selected from hydrogen, alkyl (C1 -C8), cycloalkyl, substituted or unsubstituted aryl, halogen, alkoxy (C1 -C8), aroxy, cycloalkoxy, dialkylamino including symmetrical and unsymmetrical alkyl groups with one to eight carbon, alkylcycloalkylamino, dicycloalkylamino, STR3 wherein Z is hydrogen, alkyl (C1 -C8), substituted or unsubstituted aryl, aralkyl, aroxyalkyl, alkoxyalkyl or halogen.
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(2008/06/13)

Process for preparing 6-alkoxy-5-trifluoromethyl-1-naphtoic acids and novel 1-cyano-naphtalene intermediates
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-
(2008/06/13)

Substituted dibenzothiophenes
This disclosure described novel derivatives of dibenzothiophene, dibenzothiophene sulfoxide, dibenzothiophene sulfone, thioxanthene, thioxanthene sulfoxide and thioxanthene sulfone which are active as modulators of the mammalian immune response system.
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(2008/06/13)

Stabilization of tris(trifluoromethyl)borane in complexes with primary, secondary and tertiary amines. Crystal and molecular structure of (CF3)3B*NHEt2 and (CF3)3B*NH2Et
Various adducts (CF3)3B*NHR1R2 of the unknown free Lewis acid tris(trifluoromethyl)borane with secondary amines have been prepared from Cl2BNR1R2 by nucleophilic trifluoromethylation with CF3Br/P(NEt2)3 and subs
Brauer, D.J.,Buerger, H.,Doerrenbach, F.,Krumm, B.,Pawelke, G.,Weuter, W.
p. 161 - 172
(2007/10/02)

Trifluoroamine oxide: Reactions with phosphorus compounds and selected elements
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Gupta,Kirchmeier, Robert L.,Shreeve, Jean'ne M.
p. 573 - 574
(2008/10/08)

Fluorination of boron chlorides and boron bromides by reaction with bis(trifluoromethyl)mercury, trichlorofluoromethane, or tribromofluoromethane: Synthesis of BF2B5H8
The interaction of BCl3 with excess CFCl3 has been examined by 11B and 19F NMR. Although small amounts of BFCl2 and BF2Cl, 9% each, are observed after 283 h at 65°C, BF3 is not a major product. At 130°C, however, BF3 is formed in 89% yield after 33 h. Boron trifluoride is isolated in 98 and 97% yields from the reactions of BCl3 and BBr3, respectively, with CFBr3 at 130 °C. At ambient temperature, Hg(CF3)2 reacts with BCl3 and BBr3, generating BF3 in 99 and 98% yields, respectively. The reaction of B2Cl4 with excess CFCl3 was followed spectroscopically at 65, 90, and 130°C, and the 19F chemical shifts of the partially fluorinated diboron tetrahalides have been assigned. Diboron tetrafluoride was isolated from the reaction between B2Cl4 and CFBr3 in 89% yield, from B2Br4 and CFBr3 in 78% yield, and from B2Cl4 and Hg(CF3)2 in 89% yield. Within 45 min the reaction between 1-BCl2B5H8 and Hg(CF3)2 produces the new compound 1-BF2B5H8 in 96% yield. Tetraboron tetrachloride is by far the least reactive of the boron chlorides examined.
Saulys,Castillo,Morrison
p. 1619 - 1624
(2008/10/08)

Metallorganische Lewissaeuren. XL. Ein ?,?-vinylverbrueckter Dirheniumkomplex 1:η2-CH=CH2)Re(CO)5>+BF4-
1:η2-CH=CH2)Re(CO)5>+BF4- (1) is formed by reaction of (OC)5ReFBF3 with Me3SiCH=CH2. 1 reacts with Re(CO)5- or iodide to give (OC)5ReCH2CH2Re(CO)5 and +, respecti
Steil, Peter,Beck, Wolfgang,Stone, F. Gordon A.
p. 77 - 82
(2007/10/02)

BORON, ALUMINUM, AND GALLIUM TRIS(TRIFLUOROMETHANESULFONATE) (TRIFLATE): EFFECTIVE NEW FRIEDEL-CRAFTS CATALYSTS.
Boron, aluminum, and gallium tris(trifluoromethanesulfonate) (triflate) were prepared from the corresponding chlorides (bromides) and triflic acid. The group IIIA triflates were isolated in pure form and fully characterized (elemental analysis, molecular weight, and NMR and IR spectroscopy). Boron tris(triflate) is a monomeric, relatively volatile compound left bracket mp 43-45 degree C, bp 68-73 degree C (0. 5 Torr) right bracket , whereas aluminum and gallium triflate are associated, high-melting associated solids. Boron, aluminum, and gallium tris(triflate) are efficient new Friedel-Crafts catalysts as shown in alkylation, isomerization, and acylation reactions. Alkylation of benzene and toluene with methyl, ethyl, isopropyl, and tert-butyl halides (fluoride, chloride, and bromide) were carried out with boron, aluminum, and gallium tris(triflate) as catalyst in CH//2Cl//2 and CH//3NO//2 solvent at room temperature.
Olah,Farooq,Morteza,Farnia,Olah
p. 2560 - 2565
(2007/10/02)

Carbonyl difluoride: A fluorinating reagent for inorganic oxides
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Mallela,Gupta,Shreeve, Jean'ne M.
p. 208 - 209
(2008/10/08)

The reaction of (trifluoromethyl)dialkylaminoboranes with HF, HCl and HBr. X-Ray structure investigation of the amineboranes (CF3)2B(X)NHMe2, X = F and OH
The reactions of CF3B(NMe2)2 (I) and (CF3)2BNMe2 (II) with HX (X = F, Cl and Br) have been investigated.Additions with preservation of the BC bonds to yield species with tetracoordinate boron, along with some BN cleavage, were observed.While I formed boro
Brauer, D. J.,Buerger, H.,Pawelke, G.,Weuter, W.,Wilke, J.
p. 293 - 304
(2007/10/02)

The chlorofluorophosphoranes PClnF5-n (n = 1-4). Gas-phase structures and vibrational analyses
The geometric structures of the mixed chlorofluorophosphoranes PClnF5-n with n = 1-4 have been determined by gas electron diffraction. P-F and P-Cl bonds lengthen with increasing F/Cl substitution, whereby in general axial bonds are more strongly affected. Angular distortions from the ideal trigonal bipyramid are small, less than 1° for equatorial-axial angles and about 2° for equatorial-equatorial angles. Normal-coordinate analyses for the title compounds based on matrix infrared spectra and Raman polarization measurements (liquid) yield consistent sets of valence force constants, which reflect the trends in structural changes in this series. In the course of these normal-coordinate analyses it has been necessary to change some assignments found in the literature.
Macho,Minkwitz,Rohmann,Steger,W?lfel,Oberhammer
p. 2828 - 2835
(2008/10/08)

Substituted naphthoic acid process
6-Alkoxy-5-trifluoromethyl-1-naphthoic acids are prepared by (1) cyanating a 6-alkoxytetralone so as to form a 6-alkoxy-1-cyano-3,4-dihydronaphthalene, (2) converting the 6-alkoxy-1-cyano-3,4-dihydronaphthalene to a naphthoic acid precursor selected from a 6-alkoxy-1-cyanonaphthalene and a hydrocarbyl 6-alkoxy-1-naphthoate, (3) halogenating the naphthoic acid precursor to the corresponding 5-halo derivative, (4) trifluoromethylating the 5-halo derivative to replace the 5-halo substituent with a 5-trifluoromethyl group, and (5) hydrolyzing the resultant product to a 6-alkoxy-5-trifluoromethyl-1-naphthoic acid. In a preferred embodiment of the invention, the process is conducted so as to prepare 6-methoxy-5-trifluoromethyl-1-naphthoic acid, which, like the other products, is known to be useful as a pharmaceutical intermediate.
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(2008/06/13)

(Trifluoromethylthioamino)boranes, IV - Preparation and Properties of nBX3-n with n = 3; n = 2, X = Cl, Br, N3, and n = 1, X = N3
Hg2 (4a) reacts with BBr3, B(SCF3)3, and BCl3 to give B3 (1) in decreasing yields.The thermal stable 1 is a very weak Lewis acid and sensitive to hydrolysis. 4a or (CH3)3SiN3 react with (CF3S)2NBX2 to form 2BX (X = Cl, Br, 2a,b) and (CF3S)2NB(N3)2 (3c), respectively, in good yields.Similarly 2a,b and (CH3)3SiN3 give 2BN3 (2c).Reactions of nEn with BX'3 (X' = F, Cl, Br, SCF3) were investigated with regard to multiple substitution at the boron atom.Empirical eva luated relative reactivities of element-nitrogen bonds and substitution series for reactions of boron compounds with HgII compounds are presented.Spectroscopical data of the newly prepared substances are discussed.
Haas, Alois,Willert-Porada, Monika
p. 1463 - 1475
(2007/10/02)

Transition Metal Compounds with the Ligand =N-TeF5
F4Mo=N-TeF5, F4W=N-TeF5, F3V=N-TeF5, Cl4Mo=N-TeF5, and Cl3V=N-TeF5 have been synthesized.All compounds 1-5 have a metal-nitrogen double bond.
Huppmann, Peter,Seppelt, Konrad
p. 457 - 461
(2007/10/02)

Process for the preparation of fluoroaromatic compounds substituted in the o-position
Ortho-substituted fluoroaromatic compounds are prepared by reaction of corresponding anilines, which are substituted in the o-position, with alkyl nitrites in the presence of alcohols and/or ethers and in the presence of boron trifluoride or boric acid esters and hydrogen fluoride, and by isolation and decomposition of the diazonium tetrafluoborate produced.
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(2008/06/13)

Synthesis and properties of ClF6BF4
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Christe, Karl O.,Wilson, William W.
p. 1950 - 1951
(2008/10/08)

Tellurium-nitrogen compounds
With H2N-TeF5 and (CH3)3SiNHTeF5 as the starting materials numerous new tellurium-nitrogen compounds have been synthesized. Almost all of them contain the >N-TeF5 group, which stabilizes many double-bonded systems such as O=C=NTeF5 and Cl4W=NTeF5. Cl2Se=NTeF5 is a rare example of a compound containing a discrete selenium-nitrogen double bond.
Hartl, Hans,Huppmann, Peter,Lentz, Dieter,Seppelt, Konrad
p. 2183 - 2187
(2008/10/08)