Conditions for the synthesis of Sb(III) fluoride complexes

Complexation of Sb(III) fluorides with alkali metal, ammonium, and thallium cations in the MF-SbF₃-H₂O systems at the molar ratios MF : SbF₃=(0.01–2) : 1 is studied by preparative chemistry, pH-metry, ₁₉F NMR, IR and X-ray powder diffraction methods. The crystals of Sb₃O₂F₅, MSb₄F₁₃, MSb₃F₁₀, MSb₂F₇, M₂Sb₃F₁₁, M₃Sb₄F₁₅, MSbF₄, M₂SbF₅ are synthesized and the factors influencing their formation are discussed. Some types of Sb(III) fluoride complexes are shown to be formed in the MX-SbF₃-H₂O systems (X = Cl^–, NO₃^–, BF₄^–, SCN^–, ClO₄^–).Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 12, 2004, pp. 833–837.Original Russian Text Copyright © 2004 by Zemnukhova, Kovaleva, Fedorishcheva, Konshin, Davidovich.     

Superionic Conduction in Complex Fluorides of Antimony(III) MnSbxFy (M—Cations of an Alkali Metal, Ammonium, or Thallium, n = 1–3, and x = 1–4)

Methods of ¹⁹F NMR and impedance spectroscopy are used to investigate the internal mobility of fluoride (ammonium) ions and electrophysical characteristics of complex trivalent antimony fluorides MSb₄F₁₃, MSb₃F₁₀, MSb₂F₇, M₂Sb₃F₁₁, M₃Sb₄F₁₅, and MSbF₄ (M is an alkali cation, ammonium, thallium). The ion motion types in the cationic and anionic sublattices of the fluorides are determined at 150–500 K. The polymorphous transformations in the fluorides are usually phase transitions to a superionic state and their high ionic (superionic) conductivity (σ ≥ 10⁻⁴ to 10⁻² S cm⁻¹ at 400 K) is due to the diffusion motion of ions of fluoride, ammonium, and possibly sodium, potassium, and thallium. The high polarizability of thallium ions favors the development of high mobility of fluoride ions in the fluorides.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 560–572.Original Russian Text Copyright © 2005 by Kavun, Uvarov, Slobodyuk, Brovkina, Zemnukhova, Sergienko.     

Hydrolysis of antimony(III) fluoride complexes

Vibrational and ¹⁷O NMR spectroscopy in combination with quantum chemical calculations are used to investigate the hydrolysis of antimony(III) fluoride complexes. A hydrolytic decomposition of SbF₃ and [SbF₄]^? is accompanied by oligomerization with the formation of edge-and corner-connected dimers ([Sb₂O₂F₄]^2?, [Sb₂OF₈]^4?) and trimers ([Sb₃O₃F₆]^3?, [Sb₃OF₉]^2?) with bridging oxygen atoms. The hydrolysis of [SbF₄]^? is also characterized by the presence in the solution of a discrete cation of [SbF₅]^2? which is least hydrolized. Only a partial isomorphic substitution of fluoride ion by hydroxide one is possible, which is reflected in the composition of K₂Sb(OH)_xF_5?x (x = 0.3) crystals isolated from the fluoride aqueous solution.     

Biological Properties of Antimony(III) Fluoride Complexes

Result of a study of how antimony trifluoride and fluoride complexes MSb₂F₇ (M = K, Rb, Cs, Tl, NH₄), MSbF₄ (M = Na, K, Rb, Cs, NH₄), and M₂SbF₅ (M = Na, K, Rb, Cs, Tl, NH₄) affect the growth of associations of marine bacteria and vital activity of marine alga Ulva Fenestrata are presented. The possible ways of using Sb(III) fluoride compounds are discussed.     

121,123Sb NQR study of antimony(III) fluoride complexes

Antimony(III) complexes with nitrogen-containing ligands: 2SbF₃·Gly, SbF₃·Gly, SbF₃·2NA, SbFO·Gly, MSb₂F₇ (M=Et₂NH₂, Bu₄N, HNA⁺), MSbF₄ (M=Et₂NH₂, Pr₂NH₂, Bu₄N, HNA⁺, HGly⁺), M₂SbF₅ (M=Et₂NH₂ and Pr₂NH₂), where Gly is glycine (⁺NH₃CH₂COO⁻) and NA is nicotinamide (β-C₅H₄NCONH₂), were studied by^121,123Sb NQR spectroscopy at 77 K. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2232–2236, November, 1998.     

Crystal structure of L-leucinium tetrafluoroantimonate(III)

The crystal structure of L-leucinium tetrafluoroantimonate(III) of the composition (C₆H₁₄NO₂)SbF₄ (orthorhombic symmetry: a = 6.1459(6) Å, b = 14.994(1) Å, c = 24.789(2) Å, Z = 8, P 2₁2₁2₁ space group) synthesized for the first time is determined. The (C₆H₁₄NO₂)SbF₄ structure represents a new structure type of tetrafluoroantimonate(III). It is formed by (C₆H₁₄NO₂)+ cations and chain complex [Sb₂F₈]_n ²ⁿ anions composed of Sb₂F₈ dimers linked into chains by bridging F atoms. The Sb₂F₈ dimers consist of SbF₃ and SbF₅ groups bound by bridging fluoride atoms of the SbF₅ group. Chains in the structure are linked by N-H…F, N-H…O, and O-H…F hydrogen bonds into a three-dimensional framework.     

Synthesis and properties of pentavalent antimony and bismuth fluorides

Properties of Sb^v and Bi^v fluorides and M^IIF₂-M^vF₅ (M^v ? Sb, Bi; M^II ? Mg, Ca, Sr, Ba), HalF₃-BiF₅ (Hal ? Cl, Br) systems have been studied. Only M_II(M^vF₆)₂ and HalF₂[BiF₆] are shown to be formed in these systems. M_II(M^vF₆)₂ and HalF₂[BiF₆] contain M^vF₆-octahedra in their crystal lattices. SbF₅ is found to be a stronger Lewis acid than BiF₅ and to be capable to substitute the latter in its fluoro complexes. BiF₅, in contrast to SbF₅, does not form polyfluoro anions (e.g.MF₁₁-etc.). The thermal stability of Sb_v and Bi_v fluorides and their transformations at high temperature were studied.     

Synthesis and crystal structure of new sodium oxothiocyanofluoroantimonate(III) Na2Sb5F9O3(NCS)2

Na₂Sb₅F₉O₃(NCS)₂, a new complex, has been synthesized from NaSCN and SbF₃ aqueous solutions and studied by chemical, X-ray diffraction, and thermal analyses and IR, ^121,123Sb NQR, and ¹⁹F NMR spectroscopy. Its layered structure (triclinic symmetry system, a = 6.9998(1) Å, b = 9.4180(1) Å, c = 13.1094(2) Å, α = 74.815(1)°, β = 78.188(1)°, γ = 82.779(1)°, Z = 2, space group P $\bar 1$ ) is built of Na⁺ cations and [Sb₁₀F₁₈O₆(NCS)₄]^4? decanuclear complex anions that consist of two [Sb₅F₉O₃(NCS)₂]^2? pentanuclear complex anions linked by two weak Sb-F ionic bonds (2.529(2) Å). Decanuclear complex anions are linked into layers by secondary Sb…F bonds and Na-F bonds. Van der Waals interactions link these layers into a framework. The complex is stable up to 200°C.     

Recent achievements in the synthesis and characterization of metal hexafluorantimonates and hexafluoroaurates

The efforts to prepare new MSbF₆/MSb₂F₁₁ (A = In, Cu, Au, Hg) compounds were partly successful. Reaction between InBF₄ and excess SbF₅ in anhydrous hydrogen fluoride (aHF) yields a mixture of InF₃·3SbF₅ and unidentified SbF₃·xSbF₅. The attempts to synthesize MSbF₆/MSb₂F₁₁ salts (A = Au, Hg) by controlled reduction of Au(SbF₆)₂ or Hg(SbF₆)₂ solutions in aHF/SbF₅ by elemental hydrogen, resulted in the precipitation of metallic Au or Hg₂(Sb₂F₁₁)₂. In the reaction of metallic Cu and deficit SbF₅, the synthesis of CuSbF₆ was achieved. CuSbF₆, like CuAsF₆, is a rare example of a Cu(I) compound in a pure fluorine environment.Vibrational spectra of M(II) hexafluoroantimonates (M = Ni, Fe, Co, Cu, Cr, Pd, Ag) were reinvestigated. It was found that many of them originally assigned to M(SbF₆)₂ compounds, belong to their mixtures with oxonium salts H₃OM(SbF₆)₃, H₃OSbF₆, and/or H₃OSb₂F₁₁.Reactions were studied between MF₂/2AuF₃ (M = Ni, Cu, Ag, Zn, Cd and Hg) and KrF₂ or UV-irradiated elemental fluorine in aHF as solvent at room temperature. On the basis of mass balances, Raman spectroscopy and X-ray powder diffraction analysis it can be concluded that the isolated solids have structures that can be considered in terms of an M(AuF₆)₂ formulation. Previously reported syntheses and characterization of M(AuF₆)₂ (M = Mg, Ca, Sr, Ba) were reinvestigated. In the case of M = Ba two different Au⁻F₆ salts were isolated.Raman spectra of the majority of synthesized metal hexafluoroaurates (M = Ni, Cu, Ag, Zn, Cd, Hg, Mg and Ca) show more bands than expected for regular Au⁻F₆ anion, indicating that the salts obtained exhibit relatively strong cation-anion interactions. The Raman spectra of the remaining Sr and Ba salts show the presence of more regular Au⁻F₆ octahedra, indicating weak cation-anion interactions.     

NMR Study of the Reactions of Tin(II) Difluoride and Antimony(III) Trifluoride with Niobium Pentachloride

The reactions of SnF₂and SbF₃with NbCl₅in acetonitrile or dimethyl sulfoxide were studied by ¹⁹F, ⁹³Nb, and ¹¹⁹Sn NMR spectroscopy. The products of reaction in acetonitrile are anionic, while those in di-methyl sulfoxide are neutral octahedral niobium chlorofluoride complexes. Tin(II) difluoride and antimony(III) trifluoride are powerful sources of fluoride ions in the preparation of metal chlorofluoride and fluoro complexes.     

Donor-Stabilised [SbF4]+: SbF5 as a Fluoride-Ion Donor

Antimony pentafluoride is a strong Lewis acid and fluoride-ion acceptor that has not previously demonstrated any discreet fluoride-ion donor properties. The first donor-stabilised [SbF₄]⁺ cations were prepared from the autoionisation of SbF₅ in the presence of bidentate N-donor ligands 2,2’-bipyridine (bipy) and 1,10-phenanthroline (phen) as their [SbF₆]⁻ salts. The [SbF₄(N−N)][Sb₂F₁₁] (N−N=bipy, phen) salts were synthesised by the addition of one equivalent of SbF₅⋅SO₂ to [SbF₄(N−N)][SbF₆] in liquid SO_2. The salts show remarkable stability and were characterised by Raman spectroscopy and multinuclear NMR spectroscopy. The crystal structures of [SbF₄(phen)][SbF₆] ⋅ 3CH₃CN and [SbF₄(phen)][SbF₆] ⋅ 2SO₂ were determined, showing distorted octahedral cations. DFT calculations and NBO analyses reveal that significant degree of electron-pair donation from N to Sb stabilizes [SbF₄]⁺ with the Sb−N bond strength being approximately two thirds of that of the Sb−F bonds in these cations and the cationic charge being primarily ligand-centred.     

Ionic mobility and electrophysical properties of solid solutions in PbF<Subscript>2</Subscript>–SbF<Subscript>3</Subscript> and PbF<Subscript>2</Subscript>–SnF<Subscript>2</Subscript>–SbF<Subscript>3</Subscript> systems

Ionic mobility and electrical conductivity of solid solutions with fluorite structure, obtained with solid-state approach in PbF₂–SbF₃ and PbF₂–SnF₂–SbF₃ systems, are studied by 19F NMR and electrochemical impedance spectroscopy methods. The 19F NMR spectra parameters, types of ion motions in the fluoride sublattice, and the ionic conductivity magnitude are shown to be determined by the temperature and fluoride concentration in the solid solutions. The solid solution specific conductivity in the PbF₂–SbF₃ and PbF₂–SnF₂–SbF₃ systems at 420–450 K is as high as ~10^–2 S/cm, which allows accounting the solid solutions as a base for preparation of functional materials.     

Crystal structure and <Superscript>121,123</Superscript>Sb NQR parameters of ammonium tridecafluorotetraantimonate(III) NH<Subscript>4</Subscript>Sb<Subscript>4</Subscript>F<Subscript>13</Subscript>

(NH₄)Sb₄F₁₃ crystals (I) are synthesized and their crystal structure (tetragonal crystal system: a = 9.6431(2) Å, c = 6.5503(2) Å, V = 609.11(3) ų, Z = 2, d _calc = 4.100 g/cm³, F(000) = 664, space group I4?) is determined. The main structural units of I are tetranuclear anionic [Sb₄F₁₃]^? complexes and [NH₄]⁺ cations. The anionic complexes are built of four SbF₃ groups linked together by tetrahedral bridging fluorine atom. At room temperature the (NH₄)Sb₄F₁₃ crystals are isostructural to previously studied МSb₄F₁₃ (М = K, Rb, Cs, and Tl). The study of ^121,123Sb NQR spectra of compound I is performed in a range of 77-370 K, which shows that when the temperature decreases (<250 K) the substance exhibits piezoelectric properties, as do other compounds of this group, but with a violation of their isostructurality.     

Ionic Mobility, Phase Transitions, and Electric Conductivity in Ammonium Tetrafluoroantimonate and Heptafluorodiantimonate(III)

The dynamics of the fluoride and proton sublattices and the electrophysical properties of NH₄SbF₄ (I) and NH₄Sb₂F₇ (II) in the temperature range 210-435 K were studied by ¹⁹F and ¹H NMR and impedance spectroscopy. Types of ionic motion were determined and their activation energies were estimated. The structural phase transitions in I and II form the high-temperature modifications -NH₄SbF₄ and -NH₄Sb₂F₇, having high ionic (superionic) conductivity in the range 425-435 K (1.9-1.5×10^-3 S/cm).     

121,123Sb NQR study of solid phases formed in systems (MF)1−x −(M′F) x −SbF3−H2O (M, M′=Na, K, Rb, Cs, and NH4)

Crystalline substances formed in the (MF)_1−x −(M′F) _x −SbF₃−H₂O systems (M, M′=Na, K, Rb, Cs, and NH₄;x=0 to 1) were investigated by^121,123Sb NQR spectroscopy at 77 K. The formation of individual Sb^III complexes NaCs₃Sb₄F₁₆·H₂O and NaKSbF₅·1.5H₂O, and statistically disordered mixed crystals M_1−x −M′ _x −SbF₄ (M, M′=K, Rb, Cs, and NH₄) was established. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 109–112, January, 1999.     

Darstellung,spektroskopische Charakterisierung und Kristallstruktur von (CF3)2C(F)OH2+Sb2F11–

Preparation, Spectroscopic Characterization, and Crystal Structure of (CF₃)₂C(F)OH₂⁺Sb₂F₁₁^– Hexafluoroacetone, (CF₃)₂CO, reacts at –78 °C with the superacid HF/SbF₅ under formation of the primary oxonium salt, (CF₃)₂C(F)OH₂⁺Sb₂F₁₁^–, which is characterized by vibrational spectroscopy and NMR spectra. The salt crystallizes in the triclinic space group P1 with a = 817.9(1), b = 989.0(1), c = 1003.8(1) pm and 2 formula units per unit cell.     

The synthesis and vibrational spectra of the antimony(V)fluoride-fluorosulfates SbF3(SO3F)2, SbF4(SO3F) and Sb2F9(SO3F)

The synthesis of the title compounds by a variety of routes is described. These routes involve the oxidation of antimony(III)fluoride by bis(fluorosulfuryl)peroxide and the use of non-statistical ligand redistribution reactions. Complex formation with ClO₂SO₃F leads to ClO₂[SbF_n(SO₃F)_6-n], with n=3 or 4. Polarized Raman data and low temperature infrared data are reported. All antimony(V)fluoride-fluorosulfates are found to have fluorosulfate bridges with SbF₃(SO₃F)₂ and SbF₄(SO₃F) being polymers. Ionic formulations for the ClO⁺₂ complexes are again based on vibrational spectra.     

Stabilization of [WF5]+ by Bidentate N‐Donor Ligands

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.     

Anionische Antimon(III)-Fluorokomplexe mit protonierten Azakronenethern als Gegenionen. Strukturen und Mößbauerspektren von [H2cyclam]2[Sb4F16] · 2 H2O, [H4cyclam][Sb2F10] · 2 HF und [H4(tetramethyl)cyclam]2[Sb4F15][HF2][F]4 (cyclam = 1,4,7,11-Tetraazacyclotetradecan)

Anionic Antimony(III) Fluoro Complexes with protonated Azacrownethers as Counterions. Crystal Structures and Mößbauer Spectra of [H₂cyclam]₂[Sb₄F₁₆] · 2H₂O, [H₄cyclam][Sb₂F₁₀] · 2 HF, and [H₄(tetramethyl)cyclam]₂[Sb₄F₁₅][HF₂][F]₄ (cyclam = 1,4,7,11-Tetraazacyclotetradecane) The title compounds are formed by reaction of SbF₃ with the respective azacrownether. [H₂cyclam]₂[Sb₄F₁₆] · 2 H₂O contains tetrameric anions which weakly associate to chains. The [H₂cyclam]²⁺ ions possess an unusual conformation due to intramolecular hydrogen bonds. [H₄cyclam][Sb₂F₁₀] · 2HF contains the dimeric hitherto unknown [Sb₂F₁₀]^4? ion; two HF molecules are attached to it by hydrogen bonds. The structure of [H₄(tetramethyl)cyclam]₂[Sb₄F₁₅][HF₂][F]₄ is made up of the two dimensional polymeric [HSb₄F₁₇]^4? anion. The tetra-protonated tetramethylcyclam ions form host-guest complexes with fluoride ions.     

Synthesis,characterization and thermal decomposition of Sb<Superscript>III</Superscript>-M-Sb<Superscript>III</Superscript> type trinuclear complexes of ethylenediamine-N,N, N′, N′-tetraacetate (<Emphasis Type="Italic">M</Emphasis>:Co(II), La(III), Nd(III), Dy(III))

Four ethylenediamine-N,N,N′,N′-tetraacetate complexes with Sb(III)-M-Sb(III) polynuclear structure (M=Co(II), La(III), Nd(III), Dy(III)) are synthesized. [Sb₂-μ₄-(EDTA)₂Co(H₂O)₂]·5.15H₂O is characterized by single crystal X-ray diffraction. The crystal structure of [Sb₂-μ₄-(EDTA)₂Co(H₂O)₂]·5.15H₂O belongs to monoclinic system, space group P2₁/n, lattice parameters: a=6.9969(2), _b=20.8705(4), _c=10.8106(2) Å, β=90.031(1)°, _V=1578.66(6) ų, _Z=2, _{M r}=1007.76, _{D c}=2.120 g cm^?3, _F(000)=1001, μ=2.323 mm^?1, the final _R=0.0235 and _wR=0.0629 for 3480 observed reflections (_I>2σ(_I)). The powder X-ray diffraction patterns of the complexes are also measured. Elemental analyses, FTIR spectra, TG-DSC and DTA of [Sb₂(EDTA)₂Ln]NO₃·_nH₂O are performed. FTIR spectra reveal that the antimony and other metallic ions were connected through the carboxylate bridges. The thermal analysis can demonstrate the complex formation of the antimony, other metallic ions and EDTA. The possible pyrolysis reactions in the thermal decomposition process of the complexes, the experimental and calculated percentage mass losses are also given.