Antimony Trifluoride Research Articles

Construction of Fluoride‐Rich Interphase for Sustained Magnesiophilic Site Release Toward High‐Stability Chloride‐Free Magnesium Metal Batteries

AbstractRechargeable magnesium batteries (RMBs) have the potentials in terms of high energy density, resource abundancy and safety beyond current lithium‐ion batteries. However, the bare Mg metal electrode is prone to be passivated by solvents, suffering from the extremely high overpotential and short life during cycling. Herein, a facile chloride‐free solution pretreatment method for Mg anode is developed to construct the fluoride‐rich artificial interphase. Driven by the strong‐Lewis‐acidity trifluoromethanesulfonate anion, the interphase consisting of magnesiophilic and fluoride‐rich components are constructed by the substitution reaction of Mg metal with antimony trifluoride. The formed porous Sb‐based skeletons can uniform the electric‐field distribution and Mg ions flux at anode side, inducing the self‐adapting dendrite‐free Mg deposition even under large current density. The generated alloyable metal fluoride enables to lower the desolvation energy barrier for Mg ions and sustainedly release metallic antimony to compensate for the potentially invalid magnesiophilic sites during cycling. Therefore the symmetric cells with modified Mg anodes achieve the excellent cycling over 2000 h at 1 mA cm−2 and under a high areal capacity of 5 mAh cm−2. The full cells with CuS cathodes exhibit a superior high voltage stability (2.6 V vs Mg/Mg2+) and high coulombic efficiency close to 100%.

In-situ polymerized electrolyte from a bifunctional additive for Li+ bulk phase migration and high-flux interface transport in lithium metal batteries

As a promising candidate of next-generation high-energy storage system, lithium metal batteries (LMBs) are still hindered by safety problems mainly derived from the leakage of liquid electrolytes and growth of lithium dendrite. Hence, electrolyte design and modification of electrode interphase become a feasible strategy for future exploitation of LMBs. Critically, bulk phase migration and high-flux interface transport of Li+ present inspiration. Herein, we introduce a bifunctional initiator, antimony trifluoride (SbF3), to in-situ form poly-DOL electrolyte (PDOL, 4 mg SbF3 10DOL-1DME) and build an anode interphase containing LiF and Li3Sb alloy hybrid, of which the system has high ion conductivity (1.404 mS cm−1), required Li+ migration path and intellectualized artificial interphase film. With the guidance of fast charge transport channel and in the effort of interface functionalization, Li+ obtains fast transition channels and high-flux interfacial flow, the batteries with SbF3 display superior cycling stability. It provides an accessible method to manufacture eligible quasi-solid LMBs for improved safety application.

СATALYTIC METHOD FOR THE SYNTHESIS OF 3-HYDROXY-2-NAPHTOIC ACID ANILIDE

Arylamides of 3-hydroxy-2-naphthoic acid are widely used in the production of organic azo pigments, as medicines and pesticides.
 Titanium tetrachloride, tetrabutoxytitanium and polybutoxytitanates, previously used for the synthesis of the most important of them., 3-hydroxy-2-naphthoic acid anilide by boiling of the latter in aniline (184 °C), proved to be ineffective as catalysts in carrying out this reaction in ortho-xylene.
 The study of the reasons for this inhibition of catalysis showed that it can be associated with the interaction of Ti(4+) with the hydroxy group of 3-hydroxy-2-naphthoic acid, its oxidation, accompanied by a decrease in the effective charge of titanium.
 Taking into account this inhibition, in the search for new catalysts for the synthesis of 3-hydroxy-2-naphthoic acid anilide, the known literature data on the oxidizing ability (according to the values of the reaction rate constant k) with respect to phenoxyl radicals of a number of Lewis acids, including titanium tetrachloride, were used:
 SbCl5>TiCl4 >SnCl4>PCl5>AlCl3
 k, l·mol-1·sec-1 105 157 156 42 18.
 This made it possible to choose phosphorus trichloride as an effective catalyst. It is shown that this compound, in an amount of only 2% mole. from 3-hydroxy-2-naphthoic acid, allows in boiling ortho-xylene (145 °C), under relatively mild conditions, compared to boiling aniline (184 °С), to obtain anilide 3-hydroxy-2-naphthoic acid (by reaction of the latter with aniline) of good quality with a practically quantitative yield.
 Antimony trifluoride also has similar pro­perties as a catalyst, at the level of efficiency of phosphorus trichloride.
 The ability of catalysts to act as an oxidizing agent should, apparently, always be taken into account during the catalytic amidation of aromatic oxycarboxylic acids at elevated temperatures.

(C3N6H7)2SbF5·H2O Exhibiting Strong Optical Anisotropy from the Optimal Arrangement of π-Conjugated (C3N6H7)+ Groups.

An antimony fluoride melamine birefringent crystal, (C3N6H7)2SbF5·H2O, was obtained by introducing the π-conjugated delocalized melamine and antimony trifluoride via a simple aqueous solution evaporation method. It features one-dimensional parallel [C3N6H7]∞ chains further connected by hydrogen bonds originated from [SbF5]2- groups with lone pairs. The experimental optical band gap (4.74 eV) allows it to be used in the ultraviolet region. The first-principles calculations suggest that (C3N6H7)2SbF5·H2O exhibits a large birefringence (∼0.38@550 nm), which is twice larger than that of the commercial CaCO3 crystal. Therefore, introducing the fluoride into π-conjugated melamine may be a good tactic to obtain birefringent crystals with large optical anisotropy.

Antimony lone electronic pair as a stereoelectronic barrier to stibatrane

To examine the effect of 5s2 lone electron pair of antimony atom on the reaction of antimony trifluoride and triethanolamine in the presence of sodium methylate, the crystal structure of the reaction product -2-fluoro-6-(2-hydroxyethyl)-1,3-dioxa-6-aza-2-stibacy-cylooctane (1-fluoro-2-hydrostibatrane) FSb (OCH2CH2)2NCH2CH2OH) was confirmed. In the compound structure, the hydrogen atom of the 2-hydtoxyethyl group of each molecule forms an intermolecular hydrogen bond with the oxygen atom of one of the five-membered SbOCH2CH2N half-cycles in a neighbouring molecule. A geometry of both five-member N-C-C-O-Sb heterocycles, end-capped by transannular N→Sb bond in the 1-fluoro-2-hydrostibatrane molecule, is almost identical. C-O, C-C, N-C interatomic distances and valence angles in two endocyclic units (NCCOSb) are comparable to those observed in RSi(OCH2CH2)3N silatranes. A coordination polyhedron of the Sb atom can be represented as a transition from a bisphenoid to Sb(O3)N trigonal pyramid, with a nitrogen atom at the apex and three oxygen atoms in the base. The N→Sb transannular coordinate bond length is 2.402(4) Å, which is 0.40 Å greater than the Sb-N covalent bond standard length. The Sb-F bond (1.997(4) Å) is 0.12 Å longer than that in the SbF3 molecule, and insignificantly shorter than that of the Sb-Fax (2.028(3) Å) in the SbF3Gly crystalline complex. The fluorine atom substantially strays from the N→Sb axis to the direction of O(1) and O(2) atoms. The oxygen atom of the 2-hydroxyethyl group lies at a distance of 2.899(3) A from that of Sb, intermediate between the valence bond length and the sum of the Van der Waals radii of these atoms. Combined with the F atom position, one can assume the 1-fluoro-2-hydrostibatrane crystal structure as a “frozen” state of the SNi(Sb) type nucleophilic attack of the oxygen atom, uncompleted because of its repulsion by the 5s2 lone electronic pair of antimony atom.

Small molecule activation: SbF3 auto-ionization supported by transfer and mesoionic NHC rearrangement.

The reactivity of antimony trifluoride, SbF3, in non-polar aprotic solvents has been unexplored due to its negligible solubility. The reaction of the [SbF3(tmen)] complex (2) with the N-heterocyclic carbene, 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, (LDipp), probably leads to the formation of a neutral [(LDipp)SbF3] intermediate (3) in non-polar solvents. Mild heat treatment of the reaction mixture unexpectedly activates the SbF3 molecules to undergo the auto-ionization reaction. In this process, one of the (LDipp) ligands undergoes rearrangement into the mesoionic carbene (MIC) and further coordinates to the cation to form [(LDipp)2SbF2]+[SbF4]-, product (4). Studies have confirmed that N,N,N',N'-tetramethylethane-1,2-diamine (tmen) present in the solution is not involved in the conversion mechanism and serves solely as an auxiliary ligand to increase the solubility of SbF3. The compound (4) shows a rare pnictogen(iii) halide auto-ionization process with the first mesoionic NHC rearrangement on any metal/metalloid fluoride compound and the first reported reaction system where a N-heterocyclic carbene ligand facilitates the auto-ionization process on a fluorido substrate.

Functionalized Bis(pentafluoroethyl)phosphanes: Improved Syntheses and Molecular Structures in the Gas Phase

Abstract(C2F5)2PNEt2 represents an excellent starting material for the selective synthesis of bis(pentafluoroethyl)phosphane derivatives. The moderately air‐sensitive aminophosphane is accessible on a multi‐gram scale by treating Cl2PNEt2 with C2F5Li. Treatment with gaseous HCl or HBr yielded the corresponding phosphane halides (C2F5)2PCl and the so far unknown (C2F5)2PBr in good yields. The hitherto unknown (C2F5)2PF was obtained by treating (C2F5)2PBr with excess antimony trifluoride. Treatment of (C2F5)2PCl with Bu3SnH led to the quantitative formation of (C2F5)2PH. Deprotonation formally yielded the (C2F5)2P– anion in a form that was stabilized by coordination to mercury ions to form the complex [Hg{P(C2F5)2}2(dppe)]. An improved high‐yielding synthesis of (C2F5)2POH was achieved by treating (C2F5)2PNEt2 with p‐toluenesulfonic acid. The gas‐phase structures of (C2F5)2PH and (C2F5)2POH were determined by electron diffraction. The vibrational corrections employed in the data analysis of the diffraction data were derived from molecular dynamics calculations. Both compounds exist in the gas phase mostly as C1‐symmetric cis,cis conformers with regard the orientation of the C2F5 groups relative to the functional groups H and OH. The presence of a second conformer at ambient temperature is likely in both cases. The refined amounts of dominant conformers are 94(6) and 85(6) % for (C2F5)2PH and (C2F5)2POH, respectively. The conformational behaviour was further explored by potential energy surface scans based on DFT calculations. Important experimental structural parameters for the most stable conformers are re(P–C)average = 1.884(3) Å for (C2F5)2PH and re(P–C)average = 1.894(4) Å and re(P–O) = 1.582(3) Å for (C2F5)2POH. The different coordination properties of (C2F5)3P, (C2F5)2POH, (CF3)3P and (CF3)2POH were evaluated by complex formation with [Ni(CO)4]: the maximum achievable number of CO ligands substituted by (C2F5)3P is 1, by (C2F5)2POH is 2, by (CF3)3P is 3 and by the smallest ligand (CF3)2POH is 4.

Synthesis and structures of antimony trifluoride complexes with N-heterocyclic ligands

The reaction of SbF3 with 2,2′-bipyridyl in anhydrous methanol produces [SbF3(bipy)]·[SbF3(MeOH)], the structure of which comprises co-crystallised neutral centrosymmetric [F2(bipy)Sb(μ-F)2Sb(bipy)F2] dimers, with neutral four-coordinate [SbF3(MeOH)] units. These are linked by longer fluorine contacts, each antimony achieving a distorted seven-coordinate geometry. [SbF3(bipy)·H2O] was obtained from iPrOH solution, but hydrolysis in solution readily forms [bipyH][Sb2F7]. [SbF3(phen)], also containing seven-coordinate antimony, is produced from SbF3 and 1,10-phenanthroline in MeOH, but [SbF3(2,2′6′,2″-terpyridyl)] has a six-coordinate antimony centre (pentagonal pyramidal) with no significant intermolecular contacts to neighbouring molecules. In [SbF3(pyNO)] polymeric chains involving bridging fluorine and pyridine-N-oxide are present, again resulting in a very distorted seven-coordinate geometry at Sb. The geometries present in these N-heterocycle adducts are compared with those in pnictogen oxide and crown ether complexes. Attempts to isolate complexes of SbF3 with soft donors (PMe3, SMe2 etc.) have been unsuccessful, as were attempts to form complexes with SbF3 functioning as a Lewis base towards metal carbonyls.

Catalytic fluorination of dichloromethylbenzene by HF in liquid phase. Preparation of fluorinated building blocks

The selective fluorination by successive Cl/F exchanges of the dichloromethylbenzene, was studied in the presence of HF as the fluorinating agent. The influence of the presence of a catalyst or a basic solvent (such as dioxane, pyridine, tributylphosphate) in order to favour the fluorination was investigated. In mild conditions, (50 °C and after 1 h of reaction), the fluorination of the dichloromethylbenzene was observed and the polymerization reaction inhibited. The best results were obtained in the presence of the HF-dioxane system and antimony trifluoride as catalyst.

Unusual neutral ligand coordination to arsenic and antimony trifluoride

The preparations and spectroscopic characterisation of the hydrolytically unstable As(III) complexes, [AsF(3)(OPR(3))(2)] (R = Me or Ph) and [AsF(3){Me(2)P(O)CH(2)P(O)Me(2)}] are described and represent the first examples of complexes of AsF(3) with neutral ligands. The crystal structure of [AsF(3){Me(2)P(O)CH(2)P(O)Me(2)}] contains dimers with bridging diphosphine dioxide, but there are also long contacts between the dimers to neighbouring phosphine oxide groups, completing a very distorted six-coordination at arsenic and producing a weakly associated polymer structure. The reaction of AsF(3) with OAsPh(3) affords Ph(3)AsF(2), and no arsine oxide complex was formed. Reaction of SbF(3) with OER(3) (R = Me or Ph, E = P or As), Me(2)P(O)CH(2)P(O)Me(2) and Ph(2)P(O)(CH(2))(n)P(O)Ph(2) (n = 1 or 2) in MeOH produces [SbF(3)(OER(3))(2)], [SbF(3){Me(2)P(O)CH(2)P(O)Me(2)}] and [SbF(3){Ph(2)P(O)(CH(2))(n)P(O)Ph(2)}] respectively. The X-ray structures reveal that the complexes contain square pyramidal SbF(3)O(2) cores with apical F and cis disposed pnictogen oxides. However, whilst [SbF(3)(OER(3))(2)] (R = Ph: E = P or As; R = Me: E = As) and [SbF(3){Ph(2)P(O)CH(2)P(O)Ph(2)}] are monomeric, [SbF(3){Me(2)P(O)CH(2)P(O)Me(2)}] is a dimer with bridging diphosphine dioxides producing a twelve-membered ring, and [SbF(3){Ph(2)P(O)(CH(2))(2)P(O)Ph(2)}] is a chain polymer with diphosphine dioxide bridges. In the OAsR(3) reactions with SbF(3), R(3)AsF(2) are also formed. Notably the Sb-O(P) bonds are shorter than As-O(P), despite the covalent radii (As < Sb), consistent with very weak coordination of the AsF(3). IR and multinuclear ((1)H, (19)F and (31)P) NMR data are reported and discussed. BiF(3) does not react with pnictogen oxide ligands under similar conditions and halide exchange of bismuth chloro complexes with Me(3)SnF gave BiF(3).

1-Fluoro-2-hydrostibatrane

1-Fluoro-2-hydrostibatrane was synthesized by the reaction of antimony trifluoride with triethanolamine. The molecular structure of the compound was studied by X-ray diffraction and multinuclear magnetic resonance. The coordination polyhedron of the Sb atom is intermediate between a distorted tetrahedron (AX4E type of molecule) and a tetrahedral pyramid (AX4DE type of molecule). Diastereotopism of the geminal protons of each methylene group in the half-rings of the heterocycle, observed in the NMR spectra, vanishes at 65°C because of reversible cleavage of the N → Sb coordination bond and inversion of the nitrogen atom. The chemical environment of the OCH2 and NCH2 protons of the heterocycle and 2-hydroxyethyl protons is averaged due to the fast prototropic tautomerism at 75–120°C (in DMSO-d6).

The 1:1 adduct of antimony trifluoride with [1.5]dibenzothia-18-crown-6

In the title compound [systematic name: 6,7,9,10,12,13,15,16-octahydrodibenzo[n,q][1,4,7,10,13,16]pentaoxathiacyclooctadecine antimony(III) trifluoride clathrate], (C20H24O5S)SbF3], the components are held together via electrostatic interactions between the antimony lone pair and the collective electron system of the macrocycle. The antimony trifluoride molecule is situated in a perching mode above the macrocyclic cavity, its coordination being completed by three crown ether O atoms at distances in the range 2.737 (1)–3.136 (1) Å. Neighboring 1:1 adducts are linked into chains via C—H...F hydrogen bonds.

19F NMR Study of the Anion Mobility in Tin Fluorozirconate Glasses of SnF2–ZrF4–LiF and SnF2–ZrF4(HfF4)–SbF3Systems

The influence of the concentration of lithium and antimony(III) fluorides on the ion mobility in the fluoride Subscriptsystem of tin fluorozirconate glasses is investigated by 19F NMR spectroscopy in the temperature range 180–450 K. The types of ion motions are determined, and their activation energies are estimated. It is revealed that the introduction of antimony trifluoride into the composition of tin fluorozirconate glass leads to a decrease in the temperature of defreezing the diffusion of fluorine ions. By contrast, the presence of lithium fluoride hinders diffusion processes in the fluoride Subscriptsystem.

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.

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.

Tin(II) Difluoride and Antimony(III) Trifluoride as Fluorine Donors in Reactions with Tantalum Halides in Various Solvents

Reactions of SnF2and SbF3with TaF5and TaCl5in acetonitrile and dimethyl sulfoxide were studied by 19F and 119Sn NMR. It was found that SnF2and SbF3behave as fluorine donors for tantalum(V). The anionic and cationic tantalum fluorochloride complexes form in acetonitrile, while [TaF6]–predominates in dimethyl sulfoxide. Tin(II) occurs in solution in the form of fluorine-containing polymeric cations.

Preparation of Hollow Fibers of Tin Oxide with and without Antimony Doping

Abstract Hollow fibers of tin oxide with and without antimony doping were prepared by a chemical solution deposition technique using cotton fibers as a template. Homogeneous coating of tin dioxide undoped and doped with antimony was achieved on the organic fibers in aqueous solutions of tin difluoride and antimony trifluoride. Crystalline tin oxide hollow fibers were then obtained by removing the organic compounds with combustion in air. Since antimony-doped tin oxide annealed at 500–600 °C showed a low resistivity around 3.5 × 10−3 ohm·cm, the ceramic fibers produced by this technique have great potential as a novel conductive material.

Synthesis and Characterization of Novel Degradable Polyesters Derived from d-Gluconic and Glycolic Acids

The ring-opening polymerization of a novel heterocyclic monomer of the 1,4-dioxane 2,5-dione type, namely 3-(1,2-3,4-tetraoxobutyldiisopropylidene)dioxane-2,5-dione (DIPAGYL), derived from glycolic acid and partially protected gluconic acid, was investigated. Polymerization of DIPAGYL was carried out in the presence of either stannous octoate or antimony trifluoride. The influence of several factors on the polymerization yield and on the molecular weights of the resulting polymers was evaluated using an experimental design. The polymers obtained in the presence of antimony fluoride (polyDIPAGYL-Sb) and stannous octoate (polyDIPAGYL-Sn) had different microstructures according to the distribution of sequences of repeat units as determined by 1H NMR. The main chain of polyDIPAGYL-Sb was primarily composed of alternating g (gluconic) and G (glycolic) units. In contrast, the polymer chain of polyDIPAGYL-Sn resulted from a random distribution of the two comonomer units. The isopropylidene groups which protected...

Preparation of hexafluorodisilane

Hexachlorodisilane (formed by reacting ferrosilicon and chlorine) was fluorinated with antimony trifluoride to synthesize hexafluorodisilane. Improvements in synthesis and purification of Si 2F 6 were reported.

Thermodynamic and19F NMR studies of antimony trifluoride in water

Densities, specific heat capacities per unit volume and enthalpies of dilution at 25°C and osmotic coefficients at 37°C were measured for antimony trifluoride in water as functions of concentration. From the first three properties the apparent and partial molar volumes, heat capacities and relative enthalpies were derived. As well, pH measurements in water at 25°C and19F NMR spectra in water and methanol at 33°C were also carried out. All the thermodynamic properties together with the chemical shifts abruptly change in the very dilute concentration region (<0.1m) and, then, tend to a constant value. These trends have been rationalized through a simple model based on an equilibrium of dissociation of SbF3 into two ionic species. From the simulation of all the data it is derived that two concomitant equilibria are present in solution: the hydrolysis process of SbF3 which explains the pH values and the ionic dissociation of SbF3 which accounts for the19F NMR data.