Darstellung,Struktur und Schwingungsspektren der Oxofluorowolframate(VI) Cs2[WO3F2] und Cs3[W2O4F7]

Synthesis, Structure, and Vibrational Spectra of the Oxofluorotungstates(VI) Cs₂[WO₃F₂] and Cs₃[W₂O₄F₇] Cs₂[WO₃F₂] crystallizes from a melt with the same composition. The orthorhombic unit cell with a = 6.779(2), b = 7.668(1) and c = 11.626(3) Å, space group Pn2₁a, contains 4 formula units. The WO₃F₂^2? anion is polymer, W octahedrally coordinated according to the results of the X-ray crystal structure determination. Planar dioxodifluoro groups are linked into chains by oxygen atoms. The lengths of the W? O bonds are alternating. Cs₃[W₂O₄F₇] crystallizes trigonal, space group P3 m1, with a = 21.118(4) and c = 8.434(2) Å, Z = 9. The structure consists of two sets of crystallographically non equivalent dimeric anions with the formula [O₂F₃W? F? WO₂F₃]^3?. Part of the ligand atoms are disordered. The vibrational spectra of both compounds show the presence of cis-dioxo groups of the terminal ligands.     

Zum chemischen Transport der Wolframoxide WO2 und W18O49 mit HgI2. Experimente und Modellrechnungen

On the Chemical Transport of Tungsten Oxides WO₂ and W₁₈O₄₉ with Hgl₂. Experiments and Calculations Transport experiments with WO₂ or W + WO₂ or WO₂ + W₁₈O₄₉ show that HgI₂ is a transport agent as suitable as I₂. We observed transport rates up to 47 mg/h. We investigated the dependence of the transport rate on the concentration of the transport agent n°(HgI₂) as well as on the temperature. We also investigated the time dependence of the transport rates during transport experiments on a “transport balance”. Starting with WO₂ + W₁₈O₄₉, WO₂ is transported before W₁₈O₄₉. Thermodynamic calculations show that transport of W₁₈O₄₉ is understandable if the presence of small amounts of H₂O from the quartz glass wall are taken into consideration, while transport of WO₂ is possible with HgI₂ in the presence of H₂O as well as in absence of H₂O. is the most important reaction for the transport of WO₂.     

Hydrolysis of ammonium oxofluorotungstates: A F, O and W NMR study

Fluorine-19 and natural abundance ¹⁷O and ¹⁸³W NMR spectroscopy were employed for the characterization of aqueous solutions of (NH₄)₂WO₂F₄ and (NH₄)₃WO₃F₃. Dissolution of the (NH₄)₂WO₂F₄ complex is accompanied by its partial acid hydrolysis to give the trans(mer)-dimer, [W₂O₅F₆]⁴⁻, and unreacted cis-[WO₂F₄]²⁻. The cis(fac)-[W₂O₅F₆]⁴⁻ anion is the major soluble product resulting from the alkaline hydrolysis of (NH₄)₂WO₂F₄ along with the isolation of the solid (NH₄)₂WO₃F₂. In addition, the edge-bridging dimer, [W₂O₆F₄]⁴⁻, and the cyclic trimer, [W₃O₉F₆]⁶⁻, are also suggested as hydrolysis products. Decomposition of (NH₄)₃WO₃F₃ occurs in aqueous solution to give NH₄WO₃F.     

Thermodynamische analyse der reaktionsgleichgewichte im hochtemperaturbereich der systeme kohlenstoff-fluor-chlor/brom und wolfram-kohlenstoff-fluor-chlor/brom

The gas-phase composition of the systems C/F₂/Y₂ and W/C/F₂/Y₂(Y = Cl, Br) has been calculated using a digital computer on the basis that thermodynamic equilibrium is attained at the gas/solid interface with tungsten and that the rate of reaction is not kinetically controlled.The partial pressures of the various components, i.e. CX, CX₂, CX₃, CX₄, C₂X₂, C₂X₄, C₂X₆ and WX, WX₂, WX₄, WX₅, WX₆, together with those of W, X₂ and X (where X = F, Cl, Br) have been evaluated as a function of the temperature and of the halogen concentration in the input gas. While compounds of the type C_nX_m are quite stable in C/F₂/Y₂ systems, they are relatively unstable in the presence of solid tungsten where the corresponding tungsten compounds are formed.From the temperature dependence of the mass balance of tungsten, the direction of the chemical transport reactions in these systems may be predicted. In W/C/F₂/Y₂ systems, two points of inversion exist as in the tungsten-fluorine system. At low temperatures, transport proceeds down the temperature gradient, reversing its direction at moderate temperatures and proceding down the temperature gradient once more at high temperatures.     

The Mixed Valence Tungsten(IV,V) Compound Na[W2O2Br6]

The reaction of W₆Br₁₂, NaBr, and WO₂Br₂ in the presence of Br₂ in a sealed silica tube yields Na[W₂O₂Br₆] together with WOBr₄ and WO₂Br₂ in the low temperature zone (temperature gradient 1030/870 K). Na[W₂O₂Br₆] crystallizes orthorhombically in the space group Immm (no. 71) with a = 3.775 Å, b = 10.400 Å, c = 13.005 Å and Z = 2. Pairs of condensed trans-[WO₂Br₄] octahedra with a common Br₂ edge form along [100] double chains [W₂O_4/2Br₆]^1– via the oxygen atoms. The mixed valent tungsten atoms are bonded to W₂ pairs with a 2 c–3 e bond (d(W–W) = 2.946 Å, d(W–O) = 1.888 Å, d(W–Br^b) = 2.537 Å, d(W–Br^t) = 2.535 Å, ∢O–W–O = 177.4°, ∢Br^b–W–Br^b (endocyclic) = 109.0°). The Na⁺ cations connect the anionic double chains to form two-dimensional layers parallel (001), which interact by van der Waals forces. The cations are eightfold coordinated by a cube of the terminal Br^t ligands of the polymeric anions (d(Na–Br) = 3.138 Å). Na[W₂O₂Br₆] may be discussed as an intercalation compound of the oxide bromide WOBr₃.     

Notes on phases occurring in the binary tungsten-oxygen system

The phases occurring in the binary tungsten-oxygen system in the composition region WO₃WO₂ have been clarified by electron microscopy and powder X-ray diffraction in the temperature range from 723 to 1373 K. There are five structure types in the binary system, besides WO₃, viz., the {102} CS structures, the {103} CS structures, W₂₄O₆₈, W₁₈O₄₉, and WO₂. The {102} and {103} CS structures, and W₂₄O₆₈ structures, were always disordered and true equilibrium was not achieved even after 5 months of heating at 1373 K. The lowest temperature for the formation of the CS phases was of the order of 873 K, and the disordered W₂₄O₆₈ structure formed at somewhat higher temperatures. The formation of the latter phase was also slower than the formation of the CS phases. The results suggest that elastic strain energy is of importance in controlling the microstructures found in the nonstoichiometric regions.     

Zur Präparation und Struktur gemischtvalenter Niob-Wolframoxide der Zusammensetzung (Nb,W)17O47

Preparation and Structure of Niobium Tungsten Oxides (Nb,W)₁₇O₄₇ with Mixed Valency The formal substitution of 2Nb⁵⁺ by Nb⁴⁺ or W⁴⁺, respectively, and W⁶⁺ leads to tungsten niobium oxides (Nb,W)₁₇O₄₇ with mixed valency. The phases Nb_8-nW_9+nO₄₇ with n = 1 to 5 could be obtained by heating (1 250°) mixtures of NbO₂ or WO₂, respectively, with Nb₂O₅ and WO₃. The products crystallize with the structure of Nb₈W₉O₄₇. This is proved by X-ray powder diffraction and transmission electron microscopy. A further decrease of the Nb-content results in two-phase products.     

Zum chemischen Transport von Wolfram mit HgBr2 – Experimente und Modellrechnungen

On the Chemical Transport of Tungsten using HgBr₂ – Experiments and Thermochemical Calculations Using HgBr₂ as transport agent tungsten migrates in a temperature gradient from the region of higher temperature to the lower temperature (e.g. 1 000 → 900°C). The transport rates were measured for various transport agent concentrations (0.64 ? C(HgBr₂) ? 11.74 mg/cm³; T? = 950°C) and for various mean transport temperatures (800 ? T? ? 1 040°C). Under these conditions tungsten crystals were observed in the sink region. To observe the influence of tungsten dioxide (contamination of the tungsten powder) on the transport behaviour of tungsten, experiments with W/WO₂ as starting materials were performed. According to model calculations the following endothermic reactions are important for the migration of tungsten: In the presence of H₂O or WO₂ other equilibria play a role, too. Using a special “transport balance” we observed a delay of deposition of tungsten (e.g. T? = 800°C; 15 h delay of deposition) with W and W/WO₂ as starting materials. The heterogeneous and homogeneous equilibria will be discussed and an explanation for the non equilibrium transport behaviour of tungsten will be given.     

Structure and “oxidation behavior” of W24O70, a new member of the {103} CS series of tungsten oxides

Reduced tungsten trioxide crystals WO_3?x, formed by vapor transport from a preparation with bulk composition WO_?2.90, have been studied by X-ray diffraction and electron microscopy. A single-crystal X-ray investigation showed the existence of the ordered {103} CS-structure W₂₄O₇₀, a new member of the homologous series W_nO_3n?2. Electron diffraction patterns of crystal fragments, with a few exceptions, showed the presence of the W₂₄O₇₀ phase (composition WO_2.917). Lattice images, however, indicated a fairly ordered {103} CS-phase, W₂₄O₇₀, intergrown with slabs of WO₃ giving gross compositions of the examined crystals in the range WO_2.93WO_2.96. The wide WO₃ slabs were probably formed by an oxidation process during the preparation.     

Beiträge zur Untersuchung anorganischer nichtstöchiometrischer Verbindungen. XX. Metastabile Oxydation von Mischkristallreihen — ein Zugang zu W-reichen Blockstrukturen im System Nb2O5/WO3

Contributions to the Investigation of Inorganic Non-stoichiometric Compounds. XX. Metastable Oxidation of a Series of Solid Solutions — an Access to W-rich Block Structures in the System Nb₂O₅/WO₃ The characteristical region of existence of block structures with building elements that are limited in size in two directions ends in the system Nb₂O₅/WO₃, as was shown by previous investigations, under conditions of equilibrium at a maximum value of 2.654 O/ΣM. For the occurring phases with the ratios Nb₂O₅: WO₃ = 6:1, = 7:3, = 8:5 and = 9:8 as well we now were successful in substituting W for Nb. The original block structure and the corresponding ratio O/ΣM were preserved. The “9:8”-phase W_4/4[Nb₁₈W₇O₆₉], for example, forms solid solutions W_4/4[Nb₁₁W₁₄O₆₉] leaving the size of the building elements ([5 times; 5] blocks) unchanged. Hereby the ratio W/Nb is drastically enhanced from 0.444 to 1.364. By metastable oxidation of these solid solutions at temperatures of about 500°C, for instance in air, one comes back to the system Nb₂O₅/WO₃. In this way the region of existence of block structures could be expanded far beyond the limit at 2.654 O/ΣM to higher W/Nb values.     

Study on mechanism of hydrogen adsorption on WO3, W20O58, and W18O49

The density functional theory (DFT) calculation of hydrogen adsorption on tungsten oxides and calculation of the crystal structure of WO₃, W₂₀O₅₈, and W₁₈O₄₉ were performed_. These calculations suggest that the length of W-O bonds in WO₃ are 1.913 Å, the length of 66% W-O bonds in W₂₀O₅₈ is 1.8 to 1.9 Å, and the length of 43.48% W-O bonds in W₁₈O₄₉ is longer than 2.0 Å. The hydrate (WO₂[OH]₂), as an autocatalyst in the hydrogen reduction process, was found in the particular adsorption configuration of W₁₈O₄₉. The WO₃ and W₂₀O₅₈ were completely reduced within 40 to 60 minutes at a temperature of 1000°C and at a hydrogen flow rate of 200 mL/min, while W₁₈O₄₉ was completely reduced within 20 to 40 minutes. The phase composition and micromorphology of raw material and production were studied by both X-ray diffraction analysis (XRD) and FE-SEM technology. The differences of the mechanism of hydrogen adsorption on WO₃, W₂₀O₅₈, and W₁₈O₄₉ were explored based on the density functional theory calculation and the hydrogen reduction experiments.     

Growth of KY(WO4)2 single crystal: investigation of the WO3 rich region in the K2O-Y2O3-WO3 ternary system. 2 — The KY(WO4)2 crystallisation field

In order to determinate the best crystal growth conditions for KY(WO₄)₂ single-crystals, the investigation of the K₂O-Y₂O₃-WO₃ ternary system was undertaken by the study of three isoplethic sections (K₂W₄O₁₃-Y₂O₃, K₂WO₄-KY(WO₄)₂, K₂W₂O₇-KY(WO₄)₂). The stability domain and the crystallisation field of the compound were then defined: KY(WO₄)₂ is not stoichiometric and melts congruently for the composition 0.81(K₂O.4WO₃)−0.19Y₂O₃ The low temperature phase belongs to the monoclinic system (s.g. C2/c) with a=10.65(1)Å, b=10.34(1)Å, c=7.54(1)Å, β=130.5(1)°. Its crystallisation field was delimited in temperature and composition: an α-KY(WO₄)₂ crystal can grow if x_Y2O3≤0.175.     

Reactions of coordinated trimethylphosphite with binary fluorides

Fluorination of free trimethylphosphite by phosphorus pentafluoride or tungsten hexafluoride involves complex formation followed by rapid F-for-OCH₃ exchange and Michaelis-Arbusov rearrangement reactions (D.W.A. Sharp et al., $\text{J. Chem. Soc. A}$, 1969, 872; J.M. Winfield et al., $\text{ibid}$, 1970, 501). Reactions between WF₆ or PF₅ and P(OCH₃)₃, coordinated to Fe^II (low spin d⁶-inert) or Cu^I (d¹⁰ -labile) cations in CH₃CN, counter anions PF₆^? or AsF₆^?, are very different as evidenced by an n.m.r. study.Reactions between Fe^IIP(OCH₃)₃ and WF₆ are very slow at room temperature; the major products are CH₃PF₄ and WOF₄.NCCH₃. Reactions between Cu^IP(OCH₃)₃ and WF₆ or PF₅ are rapid, even below room temperature, and depend on the stoicheiometry. The major products are W₂O₂F₉^? and a PF₅X^? species, or OPF₃, minor products include CH₃OPF₂, (CH₃O)₂PF, and PF₃. When the mole ratio coordinated P(OCH₃)₃:WF₆ is 1:1, additional W₂O₂F₉ and PF₅X n.m.r. signals are observed.The reactions involve fluorination of free P(OCH₃)₃ whose concentration in solution is limited by the metal cation, and in the reaction between PF₅ and Cu^IP(OCH₃)₃ PF₅.P(OCH₃)₃ has been identified as the initial product. Conventional Michaelis-Arbusov rearrangements are of minor importance as CH₃CN acts as a sink for CH₃⁺, but the final step in the formation of CH₃PF₄ is of this type.     

Mass spectrometric study of SF6-N2 plasma during etching of silicon and tungsten

The reaction products in the SF₆-N₂ mixture rf plasma during reactive ion etching of Si and W have been measured by a mass spectrometric method. Two kinds of cathode materials were used in this work; they were stainless steel for the Si etching, and SiO₂ for the W etching. The main products detected in the etching experiments of Si and W included SF₄, SF₂, SO₂, SOF₂, SOF₄, SO₂F₂, NSF, NF₃, N₂F₄, N_xS_y, NO₂, and SiF₄. In the W etching with the SiO₂ cathode, additional S₂F₂, N₂O, and WF₆ molecules were also obtained. The formation reactions about the novel NSF compound and the sulfur oxyfuorides were discussed.     

17O and 183W NMR studies of the paratungstate anions in aqueous solutions

¹⁷O (40.7 MHz) and ¹⁸³W (12.5 MHz) NMR spectra of aqueous Na₁₀[H₂W₁₂O₄₂]·27H₂O (1), Na₆[W₇O₂₄]·14H₂O (2) and (NH₄)₆[Mo₇O₂₄]·nH₂O solutions, as well as of 2, 1 and 0.1 M Na₂WO₄ and 2 M Li₂WO₄ solutions acidified up to P = 0.5, 1 and 1.14 have been measured. The composition of the W₇O₂₄^6? anion remains unchanged (2), its structure being similar to that of Mo₇O₂₄^6?183W NMR spectrum shows three resonances with the chemical shifts + 269.2, ?98.8 and ?178.9 ppm relative to WO₄^2? and intensity ratio 1:4:2. “Paratungstate A” produced during polycondensation of WO₄^2? at P ? 1.17 is identical with heptatungstate W₇O₂₄^6?. The [H₂W₁₂O₄₂]^10?183W NMR spectrum in the acidified 2 M Li₂WO₄ solution has four resonances with the chemical shifts in the range - 105–145 ppm and intensity ratio 1:2:1:2. As suggested by NMR data, the H₂W₁₂O₄₂^10? ? W₇O₂₄^6? transformations occur, which depend upon concentration and temperature.     

An electron microscope study of some nonstoichiometric tungsten oxides

Large crystals of WO₃ have been reduced to a composition of approximately WO_2.91 at 3 different temperatures, 950, 1000, and 1070°C. After reduction the crystals were examined by optical microscopy and transmission electron microscopy. The crystals were faulted in a variety of ways and rarely perfectly ordered. Large crystals heated at 1070°C supported oxygen loss by formation of {103} CS planes while crystals heated at 950°C contained {102} CS planes. At 1000°C {102} and {103} CS planes coexisted. It was found that the way in which the WO₃ structure accommodated oxygen loss was a function of composition and of temperature. In all experiments, some vapour transport also took place, resulting in the growth of needle shaped crystals. These were always members of the W_xO_3n?2 homologous series of oxides, and contained {103} CS planes, irrespective of the formation temperature.     

Five-component reciprocal systems Na,K∥Cl,CO<Subscript>3</Subscript>,MoO<Subscript>4</Subscript>,WO<Subscript>4</Subscript> and Na,K∥F,CO<Subscript>3</Subscript>,MoO<Subscript>4</Subscript>,WO<Subscript>4</Subscript>

Five-component reciprocal systems Na,K∥Cl,CO₃,MoO₄,WO₄ and Na,K∥F,CO₃,MO₄,WO₄ have been studied by differential thermal analysis (DTA) and X-ray powder diffraction (XPD). The systems have been triangulated to phase simplexes. The main reciprocal and complex-formation reactions have been revealed. The stability of [Na,K]₂CO₃, Na₂[Mo,W]O₄, and K₂[Mo,W]O₄ binary solid solutions and the nonexistence of quintuple invariant points in the title systems have been verified.     

Ein neuer Strukturtyp am Lanthanoid-Oxowolframat FeCe(WO4)W2O8 = FeCe(WO4)3

A New Structure Type for the Rare Earth Oxotungstate FeCe(WO₄)W₂O₈ = FeCe(WO₄)₃ Single crystals of the hitherto unknown compound FeCe(WO₄)₃ have been prepared by crystallization from melts of Fe₂O₃, CeO₂ and WO₃. It crystallizes with triclinic symmetry, space group P1 , a = 7,486(3); b = 7,528(1); c = 16,502(4) Å, α = 101,00(2); β = 96,62(3); γ = 98,62°; Z = 2. Tungsten shows octahedral and tetrahedral coordination by oxygen. The crystal structure is characterized by layers related to the Scheelite and Wolframite type. Thermogravimetric measurements led to a lost of oxygen during reaction. It results in a decrease of the oxidation states of Fe³⁺ and Ce⁴⁺ respectively, as will be discussed using magnetic measurements and calculations of the Coulomb terms of lattice energy. The structure contains a one-fold coordinated oxygen.     

High-resolution transmission electron microscopy—Investigation of vanadium-tungsten oxides prepared by chemical transport reactions

Crystalline monophasic samples of three mixed vanadium-tungsten oxides (V_0.8W_0.2)₃O₇ ? (V,W)₉O₂₁, (V_0.65W_0.35)₂O₅ ? (V,W)₁₆O₄₀, and V_0.64W_0.36O_2.60 ? V₁₆W₉O₆₅ were prepared by chemical transport reactions. The block structures of these compounds were investigated by high-resolution electron microscopy. They are built up by square blocks with [3 × 3 × ∞], [4 × 4 × ∞], or [5 × 5 × ∞] cornersharing MO-octahedra. Other block sizes were only observed as defects. The thermal behavior of the compounds was investigated.     

Structural and electronic properties of tungsten trioxides: from cluster to solid surface

Geometries and electronic structures of WO₃(001) surface and a series of stoichiometric (WO₃) _n clusters (n = 1–6) have been systematically investigated using first-principles density functional calculations. Six possible reconstructured models of WO₃(001) surface with cubic phase are explored, and the most stable configuration is the \( (\sqrt 2 \times \sqrt 2 )R45^{\circ} \) surface. The main feature of WO₃(001) surface is that the top of valence band is dominated by the 2p states of the bridging oxygen atom, rather than the top terminal oxygen. By comparing the geometrical parameters, from the structural point of view, the W₃O₉ cluster can be used as the smallest molecular prototype of the WO₃ surface. However, in terms of the electronic structure, only until W₆O₁₈, the cluster begins to appear the electronic feature of the WO₃(001) surface. This may be due to the reason that the W₆O₁₈ cluster and the top layer of WO₃(001) surface show similar “stoichiometry” if we treat two kinds of oxygen atoms as different “elements”. In addition, for the chemical reactivity, using BH₃ as a probe molecule, the W₆O₁₈ cluster also bears general resemblance to the WO₃(001) surface, and the bridging oxygen atoms in two systems are the preferred sites for the nucleophilic reaction. Therefore, our results indicate that the W₆O₁₈ cluster with a spherical buckyball structure can be viewed as the smallest molecular model to understand the properties such as catalytic activity of WO₃(001) surface.