- Reactions of (CF3)3BCO with amines and phosphines
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Reactions of tris(trifluoromethyl)borane carbonyl, (CF3) 3BCO, with ammonia yielded either a mixture of [NH 4][(CF3)3BC(O)NH2], [NH 4][(CF3)3BCN], and [NH4] 2[{(CF3)3BC(O)}2NH] or neat [NH 4]2[{(CF3)3BC(O)}2NH] depending on the reaction conditions. The salt K[(CF3) 3BC(O)NH2] was obtained as the sole product from the reaction of NH3 with K[(CF3)3BC(O)F]. A simple synthesis for cyanotris(trifluoromethyl)borates, M[(CF3) 3BCN], was developed by dehydration of M[(CF3) 3BC(O)NH2] (M = [NH4], K) using phosgene. In addition, syntheses of the tris(trifluoromethyl)boron species [(CF 3)3BC(O)NHnPr]-, [(CF 3)3BC(O)NMe2]-, and (CF 3)3BC(O)NMe3, as well as of (CF 3)3BC(O)PMe3, were performed. All species were characterized by multinuclear NMR spectroscopy. As far as neat substances resulted, IR and Raman spectra were recorded and their thermal behaviors were studied by differential scanning calorimetry. The interpretation of reaction pathways, structures, and vibrational spectra are supported by DFT calculations. The solid-state structure of K2[{(CF3) 3BC(O)}2NH]·2MeCN was determined by single-crystal X-ray diffraction.
- Finze, Maik,Bernhardt, Eduard,Willner, Helge,Lehmann, Christian W.
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- The reactivity of potassium polyfluoroaryl-, polyfluoroalkenyl-, and perfluoroalkyltrifluoroborates and their hydrocarbon analogues towards acids of different strength: A systematic study of the hydrodeboration
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The hydrodeboration of the (fluoroorgano)trifluoroborates K [RFBF3] [RF = C6F5, XCF=CF (X - F, cis- and trans-Cl, -C3F7O, cis-C2F5, trans-C4F9, -C4H9) and C6F13]and of the organotrifluoroborates K [RBF3] (R = C6H5, cis- and trans-C4H9CH=CH, C4H9 and C8H17) with CH3CO2H (100%), CF3CO2H (100 %), aqueous HF and anhydrous HF was investigated. In the alkenyltrifluoroborates K [R′=CFCFBF3] the formal replacement of BF3 by a proton occurred stereospecifically under retention of the configuration. The 19F NMR spectra of K [RFBF3] in acids indicate strong interactions of the BF3 group with protons or acid molecules.
- Bardin,Idemskaya,Frohn
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- Study on the coordination properties of [CeFx]4-x and [BFy]3-y in sulfuric acid medium by complexometric potentiometric titration
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Complexometric titration experiments were carried out in three systems of F-Ce, F-B and F-Ce-B to investigate the coordination properties of CeF x4-x and BFy3-y with ion-selective electrode as indicator. The str
- He, Jingui,Li, Yong,Xue, Xiangxin,Ru, Hongqiang,Huang, Xiaowei,Yang, He
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- Direct perfluorination of K2B12H12 in acetonitrile occurs at the gas bubble-solution interface and is inhibited by HF. Experimental and DFT study of inhibition by protic acids and soft, polarizable anions
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During the optimization of the F2 perfluorination of K 2B12H12 in acetonitrile with continuous bubbling of 20/80 F2/N2, it was discovered that (i) HF and other protic acids inhibit each of
- Peryshkov, Dmitry V.,Popov, Alexey A.,Strauss, Steven H.
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- Thermal studies of potassium tetrahydroborate?sodium tetrafluoroborate mixtures
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The KBH4?NaBF4 mixture was studied by thermal analysis (differential scanning calorimetry). Chemical analysis, X-ray powder diffraction analysis, IR spectroscopy, and 11B and 19F MAS NMR spectroscopy showed that the primary stage of the complex pyrolysis process is a metathesis reaction between components to form a new mixture, NaBH4?KBF4, the decomposition of which with the release of gaseous products and the formation of polyhedral borohydride compounds (mainly B12H12 2-) in the solid residue begins at a temperature of about 563 K. At a certain ratio between reactants in the initial mixture KBH4?NaBF4, the B12H12 2- anion can form with the material participation of the BF4 - anion.
- Saldin,Sukhovei,Savchenko,Slobodyuk,Kavun, V. Ya.
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p. 489 - 497
(2017/05/05)
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- Thermoanalytical and preparative investigations of the decomposition of potassium perfluoroorganyl(fluoro)borate salts, K[RFBF3] (RF = perfluoroalkyl, -alkenyl, -alkynyl, and -aryl groups) and K[(RF)2BF2] (RF = C 6F5 and C6F13)
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Potassium perfluoroalkenyl(fluoro)borates, K[RFBF3], (RF = CF2C(CF3), cis-CF3CFCF, and cis-C6F13CFCF) decomposed at 208-225 C (Tmax, dTG). The K[RFBF3] salts (RF = C 3F7, C6F13, trans-CF 3CFCF, and trans-C4F9CFCF) decomposed at 273-312 C (Tmax, dTG). Both groups of salts formed volatile polyfluoroorganics and K[BF4] as solid residue. The preparative thermolysis of selected prototypical salts K[RFBF3] showed that the polyfluoroorganics consisted of a mixture of internal perfluorohexenes, C6F12, and 1-H-tridecafluorohexane, C6F13H, in case of K[C6F13BF 3], and of perfluorooctynes, C8F14, and cis-C6F13CFCFH in case of K[cis-C6F 13CFCFBF3]. The salts K[(C6F5) 2BF2] and K[RFBF3] (RF = CF3CC, CF3CFCFCC, C6F5CC, C 6F5, 2,3,5,6-C5NF4) decomposed in the temperature range 249-337 C (Tmax, dTG) and mainly resulted in non-volatile polyfluoroorganics besides K[BF4]. The reaction path of the thermolysis of perfluoroalkyl-, perfluoroalkenyl-, and perfluorophenyl(fluoro)borates is discussed and compared with that of perfluorocarboxylates.
- Bardin, Vadim V.,Shundrina, Inna K.,Frohn, Hermann-Josef
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- COMPOUNDS CONTAINING PERFLUOROALKYL-CYANO-ALKOXY-BORATE ANIONS OR PERFLUOROALKYL-CYANO-ALKOXY-FLUORO-BORATE ANIONS
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The present invention relates to compounds containing perfluoroalkyl-cyano-alkoxy-borate anions or perfluoroalkyl-cyano-alkoxy-fluoro-borate anions, ((per)fluoro)phenyl-cyano-alkoxy-borate anions or ((per)fluoro)phenyl-cyano-alkoxy-fluoro-borate anions or phenyl-cyano-alkoxy-borate anions which are monosubstituted or disubstituted with perfluoroalkyl groups having 1 to 4 C atoms or phenyl-cyano-alkoxy-fluoro-borate anions which are monosubstituted or disubstituted with perfluoroalkyl groups having 1 to 4 C atoms, the preparation thereof and the use thereof, in particular as part of electrolyte formulations for dye sensitized solar cells.
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(2012/12/13)
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- Silyl-directed, iridium-catalyzed ortho-borylation of arenes. A one-pot ortho-borylation of phenols, arylamines, and alkylarenes
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The regioselectivity of the borylation of arenes catalyzed by the combination of 4,4′-di-tert-butylbipyridine (dtbpy) and [Ir(cod)Cl]2 has typically been governed by steric effects. We describe a strategy that makes use of a new substituent for ortho-functionalization to overcome this bias. We show that arenes containing hydrosilyl substituents on an atom attached to the arene ring undergo borylation at the position ortho to the hydrosilyl group. Using iridium-catalyzed formation of silyl ethers and silylamines from silanes and either phenols or arylamines, we have developed the ortho-borylation into a one-pot conversion of free phenols and monoprotected anilines into hydroxy- and amino-substituted organoboron derivatives. Copyright
- Boebel, Timothy A.,Hartwig, John F.
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p. 7534 - 7535
(2008/12/22)
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- Polyfluoroorganoboron-oxygen compounds. 5 Feasible routes to perfluoroalkyltrimethoxyborates M[CnF2n+1B(OMe) 3] (n ≥ 3)
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A well applicable preparative method for lithium perfluoroalkyltrimethoxyborates, Li[CnF2n+1B(OMe) 3] (n = 3, 4, 6), was elaborated which is based on the reaction of B(OMe)3 with CnF2n+1Li generated from C nF2n+1H and t-BuLi. Alternative perfluoroalkylation reactions of B(OMe)3 with perfluoropropyllithium generated from C3F7I and RLi, perfluoropropylmagnesium bromide, or perfluoropropyltrimethylsilane and potassium fluoride gave less satisfactory results for M[C3F7B(OMe)3]. The conversion of M[CnF2n+1B(OMe)3] salts (M = Li, BrMg) into K[CnF2n+1B(OMe)3] salts and basic properties of the new salts are reported.
- Adonin, Nicolay Yu.,Bardin, Vadim V.,Frohn, Hermann-Josef
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p. 647 - 652
(2008/10/09)
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- Bifunctional perfluoroaryl boranes: Synthesis and coordination chemistry with neutral lewis base donors
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A practical synthetic route for the preparation of the known bifunctional perfluoroaryldiborane C6F4-1,2-[B(C6F 5)2]2,1, and the new diborane C 6F4-1,2-[B(C12F8)]2, 2, that circumvents the use of toxic mercury reagents has been developed. Key intermediates and 2 have been fully characterized in solution and the solid state. Solution and structural investigations of their MeCN and THF adducts have shown that 2 is a superior Lewis acid to 1, primarily owing to the reduction in steric pressure afforded by the planar 9-borafluorene rings in 2 versus the freely rotating set of pentafluorophenyl rings in 1. The two compounds bind Lewis bases via differing coordination modes, as demonstrated by the solid-state structures of the Lewis base adducts 1·MeCN, 2·THF, and 2·MeCN. Solution studies suggest that bis Lewis base adducts are also accessible; the structures of two examples (1·(MeCN)2 and 2·(THF)2) have been determined, and their role in the dynamic solution behavior of these systems is discussed.
- Chase, Preston A.,Henderson, Lee D.,Piers, Warren E.,Parvez, Masood,Clegg, William,Elsegood, Mark R. J.
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p. 349 - 357
(2008/10/09)
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- Metathetical reactions in the system Na(K)PF6 - LiBF4 - Aprotic media
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19F NMR spectroscopy, X-ray powder diffraction, elemental analysis, and ab initio quantum chemical calculations were used to study metathetical reactions between potassium or sodium hexafluorophosphate and lithium tetrafluoroborate in a mixture of propylene carbonate (PC) - dimethyl carbonate (DMC). It was shown that the increase in size of the cations in the second coordination sphere from Na+ to K+ results in an increase of the equilibrium conversion. This is in agreement with the influence of the cation size on the solubility of tetrafluoroborates in the media investigated.
- Plakhotnyk, Andriy V.,Tarasova, Lidiya D.,Ernst, Ludger,Schmutzler, Reinhard
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p. 1840 - 1842
(2008/10/09)
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- Process for the fluorination of boron hydrides
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This invention relates to an improvement in a liquid phase process for the direct fluorination of borohydride salts including the B10H10?2and B12H12?2salts wherein said borohydride salt is contacted with fluorine, under conditions for forming said fluorinated borohydride salt. The improvement in the liquid phase process resides in effecting the fluorination of said borohydride salt in the presence of a reaction medium having an acidity between that of water and anhydrous HF. More specifically, the reaction medium should have a Hammett acidity, Ho, between 0>Ho>?11.
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(2010/02/08)
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- Reaction of arenediazonium tetrafluroborates with N,N-methylenediacryalmide in the presence of thiocyanate anions
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The reactions of arenediazonium tetrafluoroborates with N,N-methylenediacrylamide in H2O-DMF (1:3) and H2O-DMSO (1:4) in the presence of thiocyanate anions involve thiocyanatoarylation by one or two multiple bonds to give [(3-aryl-2-
- Grishchuk,Baranovskii,Gorbovoi,Ganushchak
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p. 957 - 960
(2007/10/03)
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- Reactions of arenediazonium tetrafluoroborates with 1,4-bis(acryloyloxy)butane in the presence of thiocyanate ion
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The first thiocyanatoarylation reaction with an unsaturated compound containing two isolated multiple bonds, 1,4-bis(acryloyloxy)butane, was effected. The reactions of 1,4-bis(acryloyloxy)butane with arenediazonium tetrafluoroborates occur in aqueous acet
- Gorbovoi,Baranovskii,Koval'skii,Grishchuk
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p. 1230 - 1232
(2007/10/03)
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- (Fluoroorgano)fluoroboranes and -fluoroborates. 2 [1]: Synthesis and spectroscopic characterization of potassium polyfluoroalken-1-yltrifluoroborates
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The potassium fluoroborates K[RCF=CFBF3] (R = F, Cl (cis-/trans-mixture), trans-C4F9, cis-C2F5, cis-C6F13, trans-C4H9, trans-C6H5) wer
- Frohn,Bardin
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p. 2499 - 2505
(2008/10/08)
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- (Fluoroorgano)fluoroboranes and -fluoroborates I: Synthesis and spectroscopic characterization of potassium fluoroaryltrifluoroborates and fluoroaryldifluoroboranes
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A convenient preparation of K[ArBF3] (Ar=2-C6H4F, 3-C6H4F, 4-C6H4F, 2,6-C6H3F2, 3,5-C6H3F2, 2,4,6-C6H2F3, 3,4,5-C6H2F3, 2,3,4,5-C6HF4 and C6F5) is offered and the IR and multinuclear NMR spectra of these salts are reported. Treatment of the trifluoroborate salts with BF3 in chlorocarbon solvents provides an easy synthetic route to the corresponding aryldifluoroboranes ArBF2. The multinuclear NMR spectra of ArBF2 are presented. The electron substituent effect of the [-BF3]--group shows this substituent as one of the strongest σ-electron donors, while its π-electron influence is negligible (σI=-0.32, σR=-0.07).
- Frohn,Franke,Fritzen,Bardin
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p. 127 - 135
(2007/10/03)
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- Reactions of New Osmium-Dihydride Complexes with Terminal Alkynes: Metallacyclopropene versus Metal-Carbyne. Influence of the Alkyne Substituent
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Reaction of OsH2(κ2-OCOCH3){κ 1-OC(O)CH3}(PiPr3)2 (1) with 1/2HBF4·OEt2 leads to the dimer [{OsH2(κ2-OCOCH3)(PiPr 3)2}2(μ-OCOCH3)]BF4 (2), while the reaction with HBF4·OH2 gives the aquo-derivative [OsH2(κ2-OCOCH3)(H2O)(P iPr3)2]BF4 (3). The structure of 2 in the solid state has been determined by an X-ray diffraction study. The structure consists of two OsH2(κ2-OCOCH3)(PiPr 3)2 units connected through an acetate bridge. Complex 3 reacts with phenylacetylene and 1,1-diphenyl-2-propyn-1-ol to give the metallacyclopropene complexes [OsH(κ2OCOCH3){C(Ph)CH2}(P iPr3)2]BF4 (4) and OsH(κ2-OCOCH3){C[C(OH)Ph2]CH 2}-(PiPr3)2]BF4 (7), respectively. The structure of 4 in the solid state has been determined by an X-ray diffraction study. The geometry around the metal center can best be described as a pentagonal bipyramid with the two phosphorus atoms of the phosphines occupying apical positions. The equatorial plane is defined by the hydride, the acetate ligand, and the two carbon atoms of the metallacyclopropene. Reaction of 3 with tert-butylacetylene or trimethylsilylacetylene affords the carbyne complexes [OsH(κ2-OCOCH3)(≡CCH2R)(P iPr3)2]BF4 [R = CMe3 (8), H (9)], respectively. Deprotonation of 8 and 9 with KOH gives the vinylidene derivatives OsH(κ2-OCOCH3)(=C=CHR)(PiPr 3)2 [R = CMe3 (10), H (11)]. The carbyne analogue of 8 and 9 bearing a phenyl group, [OsH(κ2-OCOCH3)(≡CCH2Ph)(P iPr3)2]BF4 (5), can be obtained upon protonation of OsH(κ2-OCOCH3)(=C=CHPh)(PiPr 3)2 (6) with HBF4· OEt2. In agreement with the experimental results, DFT (B3PW91) calculations show that the cyclopropene product is thermodynamically preferred for phenylacetylene, while the carbyne isomer is preferred for tert-butylacetylene.
- Buil, María L.,Eisenstein, Odile,Esteruelas, Miguel A.,García-Yebra, Cristina,Gutiérrez-Puebla, Enrique,Oliván, Montserrat,O?ate, Enrique,Ruiz, Natividad,Tajada, María A.
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p. 4949 - 4959
(2008/10/08)
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- Calorimetric study of alkali metal tetrafluoroborates
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Adiabatic calorimetric investigation of the low-temperature heat capacity of sodium tetrafluoroborate as well as a DSC study of the thermal behavior of potassium tetrafluoroborate and of lithium tetrafluoroborate and its hydrates were carried out. Temperatures and enthalpies of phase transitions at temperature above ambient were determined for potassium tetrafluoroborate, lithium tetrafluoroborate, and lithium tetrafluoroborate mono- and trihydrate. It was demonstrated that lithium tetrafluoroborate has only one phase transition in the solid at 300 K.
- Gavrichev,Sharpataya,Gorbunov
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p. 225 - 238
(2008/10/09)
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- Silver Trifluoride: Preparation, Crystal Structure, Some Properties, and Comparison with AUF3
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Red, diamagnetic AgF3 is precipitated from anhydrous hydrogen fluoride (AHF) solutions of AgF4- salts by addition of fluoro acids (L) such as BF3, PF5, or AsF5: AgF4-+ L → AgF3 + LF-. With additional AsF5, silver(III) is reduced: AgF3 + AsFf → AgFAsF6 + 1/2F2. Such reduction does not occur with BF3, and the latter acid is therefore preferred for the preparation of stoichiometric AgF3. AgF3 is thermodynamically unstable and, in contact with AHF, at ～20 °C, loses F2 in less than 19 h according to the equation 3AgF3 → Ag3F8 + 1/2F2. The trifluoride is isostructural with AuF3. To provide for meaningful comparisons, the structure of AuF3 was redetermined. AgF3 and AuF3 were successfully refined in space group P61-D62 (No. 178) by using the Rietveld method from time-of-flight neutron powder diffraction data from 100-mg samples contained in 2-mm capillary tubes. The 7762 observations for AgF3 yielded a = 5.0782 (2) A?, c = 15.4524 (8) A?, and V= 345.10 (2) A?3, the reliability parameters for the structure being Rwp = 6.21 and Rp = 3.83%. From the 7646 observations for AuF3, a = 5.1508 (1) A?, c= 16.2637 (7) A?, V= 373.68 (2) A?33, and Rwp = 11.21 and Rp = 7.58%. The lilver or gold atom lies at the center of an elongated octahedron with two Ag-F(1) = 1.990 (3) A?, two Au-F(1) = 1.998 (2) A?, two Ag-F(2) = 1.863 (4) A?, and two Au-F(2) = 1.868 (3) A?, the approximately square, isodimensional AF4 units being joined by symmetrical μ-fluoro bridges (two F(1) in cis relationship in the AF4 unit) to form the 61 (or 65) helical chains where Ag-F(1)-Ag = 123.2 (2)° and Au-F(1)-Au = 119.3 (2)°. The ～5-A?3 smaller formula unit volume of AgF3 compared with AuF3 and the shorter z axis interatomic distance (Ag-F = 2.540 (4), Au-F = 2.756 (8) A?) are in accord with the tighter binding of the Ag(III) d-orbital electrons evident in the strong oxidizing properties of Ag(III). Interaction of AgF+ with AgF4- (1:1) in AHF yields maroon AgIIAgIIIF5. The latter interacts with AgF3 to yield AgIIAgIII2F8, which is identical with the product of the decomposition of AgF3 at 20 °C in AHF and with the material previously described1,2 AgF3. The magnetic susceptibility for AgIIAgIII2F8 obeys the Curie-Weiss law (4-280 K) with θ = -4.2 (5) ° and μeff = 1-924 (3) μB.
- ?emva, Boris,Lutar, Karel,Jesih, Adolf,Casteel Jr., William J.,Wilkinson, Angus P.,Cox, David E.,Von Dreele, Robert B.,Borrmann, Horst,Bartlett, Neil
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p. 4192 - 4198
(2007/10/02)
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- Metallorganische Lewissaeuren. XL. Ein ?,?-vinylverbrueckter Dirheniumkomplex 1:η2-CH=CH2)Re(CO)5>+BF4-
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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.
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