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1.
Molybdenum(VI)fluoride-pentafluorotellurates(VI) and Molybdenum(VI)oxide-fluoridepentafluorotellurates(VI): MoFn(OTeF5)6?n and MoOFn(OTeF5)4?n In MoF6 fluorine can be replaced by F5TeO-groups by means of B(OTeF5)3. Rearrangement reactions and internal fluorination finally leads to MoFn(OTeF5)6?n and MoOFn(OTeF5)4?n. 相似文献
2.
Nitrosyl pentafluorotellurate(VI) . NO+OTeF5? is prepared from NOCl and Hg(OTeF5)2. It is ionic NO+OTeF5? in the solid state and in acetonitrile solution, in the gaseous state however a covalent molecule ON–OTeF5. 相似文献
3.
L.B. Handy Cathleen Benham F.E. Brinckman R.B. Johannesen 《Journal of fluorine chemistry》1976,8(1):55-67
The series of compounds (FC6H4O)nWF6-n, where n = 1-6 and F is meta or para to oxygen, has been prepared and all fluorine nmr chemical shifts determined. The W-, para-, and meta- resonances all shift upfield as a function of n with approximate relative sensitivities of 1, 1/20, and 1/30, respectively. All chemical shifts are also found to be sensitive to molecular stereochemistry, with subtituents trans to oxygen shifted to higher field than those trans to fluorine. 19F data is also reported for the complete series (C6H5O)nWF6-n 相似文献
4.
Antimony(III)pentafluoroorthotellurate has been synthesized from SbF3 and B(OTeF5)3. Contrary to a previous report it is a low melting, sublimable solid (mp = 28°, bp (0.1 torr) = 68°, 19F - NMR: AB4 spinsystem δ (A) = ?42.7, δ (B) = ?38.1, J (AB) = 186 Hz). It reacts with F2, Cl2 and Br2 to give SbF2(OTeF5)3, SbCl4+Sb(OTeF5)6? and SbBr4+ Sb(OTeF5)6? respectively. Interaction of Xe(OTeF5)2 and Sb(OTeF5)3 yields Sb(OTeF5)5, which is unstable at room temperature. Salts containing the new anion Sb(OTeF5)6? have been synthesized either from Sb(OTeF5)5 and a corresponding pentafluoroorthotellurate e.g. Sb(OTeF5)5 + NMe4+ OTeF5? = NMe4+ Sb(OTeF5)6?, or from SbCl4 Sb(OTeF5)6? and an appropriate chloride SbCl4+ Sb(OTeF5)6? + NOCl = SbCl5 + NO+ Sb(OTeF5)6?, or oxidatively, using a mixture of Xe(OTeF5)2 and Sb(OTeF5)5, e.g. C6F6 + Xe(OTeF5)2 + Sb(OTeF5)5 = C6F6+ Sb(OTeF5)6? + Xe. 相似文献
5.
F. Sladky 《Monatshefte für Chemie / Chemical Monthly》1970,101(5):1559-1570
Zusammenfassung Pentafluoro-orthotellursäure, HOTeF5, reagiert mit Xenondifluorid unter HF-Abspaltung quantitativ zu Xenon(II)-bis(pentafluoro-orthotellurat), Xe(OTeF5)2 (Schmp.: 35–37°C). Die Verbindung ist bis etwa 130°C thermisch stabil, oberhalb dieser Temperatur zerfällt sie hauptsächlich in Bis(pentafluorotellur)oxid, F5TeOTeF5, Sauerstoff und Xenon. Massenspektroskopisch konnten jedoch auch Bis(pentafluorotellur)peroxid, F5TeOOTeF5 und Verbindungen der allgemeinen Formel F5Te(OTeF4)
x
OTeF5 (x=1,2) als Zerfallsprodukte nachgewiesen werden. Röntgen-Einkristalluntersuchungen zeigen, daß Xe(OTeF5)2 eben (in bezug auf das TeOXeOTe-Skelett) gebaut ist und die F5TeO-Gruppen intrans-Stellung angeordnet sind. Das Massen-, Infrarot-, Laser-Raman- und19F-KMR-Spektrum werden untersucht.
Mit 1 Abbildung 相似文献
Xenon Chemistry, I: Xe(OTeF5)2
Xenon(II)-bis(pentafluoro-orthotellurate), Xe(OTeF5)2 (M.P. 35–37°C), is formed in quantitative yield in the reaction of pentafluoro-orthotelluric acid, HOTeF5, with Xenondifluoride. HF is evolved during the reaction. Xe(OTeF5)2 is thermally stable up to 130°C. Above this temperature it mainly decomposes to bis(pentafluoro-tellurium)oxide, F5TeOTeF5, oxygen and xenon. Mass-spectroscopically, however, bis(pentafluoro-tellurium)peroxide and compounds of the general composition F5Te(OTeF4) x OTeF5 (x=1,2) have been identified as minor decomposition products. X-ray single crystal analysis proves the TeOXeOTe entity to be planar and the F5TeO groups intrans-position. Results of mass-, infrared-, laser-Raman- and19F-NMR-spectroscopy are given.
Mit 1 Abbildung 相似文献
6.
129-Xe-NMR Spectra of Xenon Compounds. II Xenon (II) Compounds The 129Xe NMR Spectra of Xe(OSeF5)2, Xe(OTeF5)2, FXe–OSeF5, FXe–OTeF5, and F5SeO–Xe–OTeF5 have been measured and discussed. The mixed compounds FXe–OSeF5, FXe–OSeF5, FXe–OTeF5, and F5SeO–Xe–OTeF5 exist only in equilibrium with the derivatives Xe(OSeF5)2, Xe(OTeF5)2 and XeF2. Coupling of 129Xe is observed with the fluorine directly bonded at the Xenon atom, with the equatorial fluorine atoms on selenium and tellurium. and with the tellurium isotop 125Te. 相似文献
7.
Anja Wiesner Lukas Fischer Dr. Simon Steinhauer Dr. Helmut Beckers Prof. Dr. Sebastian Riedel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(44):10441-10449
Salts of the weakly coordinating anions [Ga(OTeF5)4]− as well as [Ga(Et)(OTeF5)3]− and the neutral Ga2(Et)3(OTeF5)3 were synthesized and characterized by spectroscopic methods and single-crystal X-ray diffraction. Ga2(Et)3(OTeF5)3 was formed by treating GaEt3 with pentafluoroorthotelluric acid (HOTeF5) and reacted with PPh4Cl and CPh3Cl to [PPh4][Ga(Et)(OTeF5)3] and [CPh3][Ga(Et)(OTeF5)3]. In contrast, Ag[Ga(OTeF5)4] was prepared from AgOTeF5 and GaCl3 and was used as a versatile starting material for further reactions. Starting with Ag[Ga(OTeF5)4] the substrates [PPh4][Ga(OTeF5)4] and [CPh3][Ga(OTeF5)4] were formed from PPh4Cl and CPh3Cl. 相似文献
8.
J. Burgess C.J.W. Fraser R.D. Peacock P. Taylor A. Majid J.M. Winfield 《Journal of fluorine chemistry》1973,3(1):55-61
Enthalpies of formation of the tungsten (VI) compounds WF5Cl, WF4Cl2, WF5(OMe), cis-WF4(OMe)2 and cis-WF2(OMe)4 are reported. Re-distribution and decomposition reactions in the chloride-fluoride and in the methoxide-fluoride series are discussed in the light of the thermochemical results. 相似文献
9.
Douglas Turnbull Prof. Dr. Paul Hazendonk Prof. Dr. Stacey D. Wetmore Prof. Dr. Michael Gerken 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(30):6879-6886
The enhanced reactivity of [WF5]+ over WF6 has been exploited to access a neutral derivative of elusive WF5. The reaction of WF6(NC5H5)2 with [(CH3)3Si(NC5H5)][O3SCF3] in CH2Cl2 results in quantitative formation of trigonal-dodecahedral [WF5(NC5H5)3]+, which has been characterised as its [O3SCF3]− salt by Raman spectroscopy in the solid state and variable-temperature NMR spectroscopy in solution. The salt is susceptible to slow decomposition in solution at ambient temperature via dissociation of a pyridyl ligand, and the resultant [WF5(NC5H5)2]+ is reduced to WF5(NC5H5)2 in the presence of excess C5H5N, as determined by 19F NMR spectroscopy. Pentagonal-bipyramidal WF5(NC5H5)2 was isolated and characterised by X-ray crystallography and Raman spectroscopy in the solid state, representing the first unambiguously characterised WF5 adduct, as well as the first heptacoordinate adduct of a transition-metal pentafluoride. DFT-B3LYP methods have been used to investigate the reduction of [WF5(NC5H5)2]+ to WF5(NC5H5)2, supporting a two-electron reduction of WVI to WIV by nucleophilic attack and diprotonation of a pyridyl ligand in the presence of free C5H5N, followed by comproportionation to WV. 相似文献
10.
The electronegative ligand OTeF5 has been tested on the elements Ti, Mo, W, Ta, Re, Os and others. Compounds such as OMo(OTeF5)4, W(OTeF5)6, Ta(OTeF5)5, ReO2(OTeF5)3, OsO(OTeF5)4 are prepared. While ReVII could be stabilized with OTeF5, the highest oxidation state on Osmium is VI, and Iridium probably IV. OMo(OTeF5)4 shows a regular square pyramidal structure with apical double bonded oxygen. Chemistry on the ligand NTeF5 is based on the synthesis of H2NTeF5 and R3SiNHTeF51. Other new main group derivatives are so far Cl2NTeF5, HClNTeF5, OCN-TeF5, F3PNTeF5, Cl3NPTeF5, F2SNTeF5 and Cl2SeNTeF5, the first compound with a selenium-nitrogen double bond. In the transition metal series the compounds F4MoNTeF5 and Cl4WNTeF5 (in addition to the longer known polymeric (HgNTeF51) have been prepared. Both have discrete metal nitrogen double bonds. 相似文献
11.
Angela Milinkovic Dr. Antoine Dupé Ao. Univ.-Prof. Dr. Ferdinand Belaj Univ.-Prof. Dr. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(55):e202201867
Molybdenum(VI) bis(imido) complexes [Mo(NtBu)2(LR)2] (R=H 1 a ; R=CF3 1 b ) combined with B(C6F5)3 ( 1 a /B(C6F5)3, 1 b /B(C6F5)3) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H−H, Si−H and O−H bonds. Cleavage of H2 and Et3SiH affords ion pairs [Mo(NtBu)(NHtBu)(LR)2][HB(C6F5)3] (R=H 2 a ; R=CF3 2 b ) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H2O leads to [Mo(NtBu)(NHtBu)(LR)2][(HO)B(C6F5)3] (R=H 3 a ; R=CF3 3 b ). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a . Mechanistic elucidation revealed insertion of the aldehyde into the B−H bond of [HB(C6F5)3]−. We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(LR)2][{PhCH2O}B(C6F5)3] (R=H 4 a ; R=CF3 4 b ). Catalysis occurs at [HB(C6F5)3]− while [Mo(NtBu)(NHtBu)(LR)2]+ (R=H or CF3) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC). 相似文献
12.
Xe(OTeF5)2 reacts with Sb(OTeF5)3 under the formation of [Xe2(OTeF5)3]+[Sb(OTeF5)6]-. From SO2ClF solution a yellow solvate [F5TeOXe]+·SO2ClF· [Sb(OTeF5)6]- is formed with the crystal data: a = 1028.1(1), b = 1040.9(1), c = 1780.2(3) pm, α = 98.07(1), β = 97.68(1), γ = 105.82(1)°, space group . The O-Xe···O fragment is essentially linear (176.1(2)°), and the two Xe-O distances are quite different 197.1(4) and 242.6(4) pm. 相似文献
13.
Preparation and Electrochemistry of [Nb(OTeF5)6]? and [Ta(OTeF5)6]? Complexes Nb(OTeF5)5 and Ta(OTeF5)5 react with Cs[OTeF5], [Et4N][OTeF5], and [(n-Bu)4N][OTeF5] to the corresponding Cs[M(OTeF5)6], [Et4N][M(OTeF5)6], and [(n-Bu)4N][M(OTeF5)6] complexes, (M = Nb, Ta). The electrochemical reduction of the niobium complex occurs in CH2Cl2 at ?0,69 V and in acetonitrile at ?0,60 V (vs. SCE). The tantalum complex is reduced in CH2Cl2 at ?1,52 V and in acetonitrile at ?1,42 V (vs. SCE). 相似文献
14.
The formation of negative ions in electron transfer reactions between hyperthermal alkali atoms (Na, K) and WF6 has been studied in the energy range 0–30 eV c.m. Relative cross sections and translational energy thresholds for ion pair formation have been measured, from which the following electron affinities (EA) and bond dissociation energies (D) have been derived: EA(WF6) = 3.7 eV, EA(WF5) = 1.25 eV, D(WF5—F) = 5.1 eV, D)WF5—F?) = 5.4 eV, D(WF?5—F) = 7.6 eV. Several ion molecule reactions are discussed which result in formation of secondary fragmentation ions and WF?7. 相似文献
15.
Pentafluorotellurates of Pentavalent Iodine. Electronegativities of the OTeF5 and OSeF5 Groups The compounds I(OTeF5)5 and O=I(OTeF5)3 are characterized. With the help of n.m.r. spectroscopically methods it has been shown that the mixed substituted compounds FxI(OTeF5)5–x and FxI(OSeF5)5–x exist. The substitution behaviour of the –OTeF5 and -OSeF5 ligands indicate, that those groups are more electronegative than fluorine in the sence of the valence shell electron pair repulsion model. This qualitative result is indicated also by correlation of physical data of some model compounds with known values of electronegativities. 相似文献
16.
Said El‐Kurdi Abdal‐Azim Al‐Terkawi Bernd M. Schmidt Anton Dimitrov Dr. Konrad Seppelt Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(2):595-599
WF6 reacts with phosphines R3P forming 1:1 compounds. With R=P(CH3)3 the coordination around the tungsten atom is capped trigonal prismatic, with R=P(CH3)2C6H5 the coordination is capped octahedral, as established by single‐crystal structure determinations: [(CH3)3P? WF6]: a=752.5(21), b=945.7(24), c=629.8(18) pm. β=110.36(13)°, space group Cm, Z=2; [(CH3)2(C6H5)P? WF6]: a=762.2(2), b=1123.5(2), c=2647.5(6) pm, space group Pbca, Z=8. [(CF3CH2)2N? WF5] reacts smoothly with P(C6H5)3 forming known P(C6H5)3(F)2 and [(CF3CH2)2N? WF4? P(C6H5)3], a stable, green, molecular species, identified among other methods with an crystal structure determination: a=914.9(1), b=956.0(1), c=1449.8(2) pm, α=7.642(4), β=81.648(3), γ=81.519°, space group P$\bar 1$ , Z=2. 相似文献
17.
Fluorine Exchange in Trifluorophosphine Metal Complexes. IX1. (Reactions of Tetrakis(trifluorophosphine)nickel(0) with Alkyl(trimethylsilyl)amines and Amides2) Alkylaminodifluorophosphine complexes Ni(PF3)4-n(PF2NHR)n (n = 1, 2, 3) 8–11 and Me3SiF are obtained, if alkyl(trimethylsilyl)amines NHR(SiMe3) (R?CH3 and n-C4H9) are reacted with Ni(PF3)4 ( 1 ). The mechanism of these peripheric reactions is discussed by assuming a four centered type intermediate. However reactions of 1 with the lithium amides LiNR(SiMe3) (R = CH3, C2H5, n-C4H9, and C6H5) yield LiF and the difluorotrimethylsilylaminophosphine complexes Ni(PF3)4-n[PF2NR(SiMe3)]n (n = 1, 3, 4) 12–18 . 相似文献
18.
Matthias Weil 《无机化学与普通化学杂志》2014,640(1):128-135
Two modifications of (TeO)(HAsO4) were obtained by reacting tellurium dioxide with arsenic acid under boiling conditions (modification I, acid concentration 80 wt‐%) or under hydrothermal conditions (modification II, acid concentration 50 wt‐%). The crystal structures of the two modifications were determined from single‐crystal X‐ray data [modification I: P21/c, Z = 4, a = 7.4076(10), b = 5.9596(7), c = 9.5523(11) Å, β = 102.589(8)°, 2893 structure factors, 68 parameters, R[F2 > 2σ(F2)] = 0.0247, wR2(F2 all) = 0.0530; modification II: P21/c, Z = 4, a = 6.2962(4), b = 4.7041(3), c = 13.9446(8) Å, β = 94.528(3)°, 2549 structure factors, 69 parameters, R[F2 > 2σ(F2)] = 0.0207, wR2(F2 all) = 0.0462)]. Dehydration of (TeO)(HAsO4)‐II at temperatures above 260 °C results in the formation of polycrystalline (Te3O3)(AsO4)2. Single crystals of the anhydrous product were grown either by heating stoichiometric amounts of the binary oxides TeO2 and As2O5 in closed silica glass ampoules or with higher concentrated arsenic acid (80 wt‐%) under hydrothermal conditions at 220 °C. The common features in the crystal structures of (Te3O3)(AsO4)2 [P$\bar{1}$ , Z = 4, a = 6.5548(4), b = 7.6281(6), c = 15.0464(15) Å, α = 140.212(6), β = 102.418(9)°, γ = 77.346(5)°, 5718 structure factors, 146 parameters, R[F2 > 2σ(F2)] = 0.0351, wR2(F2 all) = 0. 1093] and in that of the two modifications of acidic (TeO)(HAsO4) are [TeO5] square‐pyramids and [AsO4] tetrahedra. In anhydrous (Te3O3)(AsO4)2 and in (TeO)(HAsO4)‐II, a layered arrangement of the building units is found, whereas in the (TeO)(HAsO4)‐I structure strands are formed. Different hydrogen bonding interactions are present in the two modifications of (TeO)(HAsO4). 相似文献
19.
Tris(pentafluorophenyl)borane, B(C6F5)3 reacts with triethylaluminum, AlEt3 to a mixture of Al(C6F5)3−nEtn and Al2(C6F5)6−nEtn compounds depending on the B/Al ratio. From excess borane to excess AlEt3 the species Al(C6F5)3 → Al(C6F5)2Et Al2(C6F5)4Et2 → Al2(C6F5)3Et3 → Al2(C6F5)2Et4 → Al2(C6F5)Et5 are formed and differentiated by their para-F signal in 19F NMR. The reaction between B(C6F5)3 and the higher aluminum alkyls, tri(iso-butyl)aluminum and tri(n-hexyl)aluminum AlR3 (R = i-Bu, n-C6H13) is slower and requires AlR3 excess to shift the C6F5 R exchange equilibria to almost complete formation of Al(C6F5)R2 and BR3. At equimolar ratio the equilibrium lies on the side of the unchanged borane together with its boranate [B(C6F5)3R]− anion. For tri(n-octyl)aluminum even at large Al(n-C8H17)3 excess no C6F5 alkyl exchange can be observed, but boranate anions form. 相似文献
20.
Douglas Turnbull Stacey D. Wetmore Michael Gerken 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(37):13169-13172
Transition‐metal hexafluorides do not exhibit fluoride‐ion donor properties in the absence of donor ligands. We report the first synthesis of donor‐stabilized [MF5]+ derived from a transition‐metal hexafluoride via fluoride‐ion abstraction using WF6(L) (L=2,2′‐bipy, 1,10‐phen) and SbF5(OSO) in SO2. The [WF5(L)][Sb2F11] salts and [WF5(1,10‐phen)][SbF6]?SO2 have been characterized by X‐ray crystallography, Raman spectroscopy, and multinuclear NMR spectroscopy. The reaction of WF6(2,2′‐bipy) with an equimolar amount of SbF5(OSO) reveals an equilibrium between [WF5(2,2′‐bipy)]+ and the [WF4(2,2′‐bipy)2]2+ dication, as determined by 19F NMR spectroscopy. The geometries of the cations in the solid state are reproduced by gas‐phase geometry optimizations (DFT‐B3LYP), and NBO analyses reveal that the positive charges of the cations are stabilized primarily by compensatory σ‐electron donation from the N‐donor ligands. 相似文献