- The pseudobinary systems Bi2Ch3-Bix3 and the ternary phases on their boundary lines (Ch = S, Se, Te; X = Cl, Br, I), I: Bismuth sulfide halides
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The phase diagrams of the systems Bi2S3-BiX 3 were constructed from results of DTA and total pressure measurements and x-ray analysis. The phases: BiSCl, Bi4S 5Cl2 and Bi19S
- Oppermann, Heinrich,Petasch, Uwe
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- New routes to transition metal-carbido species: Synthesis and characterization of the carbon-centered trigonal prismatic clusters [W 6CCl18]n- (n = 1, 2, 3)
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Simultaneous reduction of WCl6 and CCl4 with bismuth metal at 400 °C affords a black solid, from which the new cluster [W6CCl18]2- is extracted into aqueous HCl. The cluster is isolated in 34% yield as (Bu4N)2[W6CCl18] and features a metal-metal bonded W6 trigonal prism centered by a carbon atom and surrounded by 12 edge-bridging and 6 terminal chloride ligands. A cyclic voltammogram of [W6CCl18]2- in DMF shows the cluster undergoes two reduction and two oxidation processes, suggesting five chemically accessible redox states. Consistent with this extensive electrochemistry, DFT calculations on the diamagnetic [W6CCl18]2- species reveal closely spaced frontier orbitals, with an a2″ HOMO situated 0.61 and 0.71 eV below unoccupied e″ and e′ orbitals, respectively. Oxidation of the cluster by a single equivalent of NO+ gives [W6CCl18]1-); which, as expected on the basis of the [W6CCl18]2- HOMO character, possesses a less elongated W6 trigonal prism. Reduction of [W6CCl18]2- with a single equivalent of cobaltocene affords [W6CCl18]2- wherein population of a low-lying e′ orbital leads to a significant Jahn-Teller distortion. Copyright
- Welch, Eric J.,Crawford, Nathan R. M.,Bergman, Robert G.,Long, Jeffrey R.
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- In-situ study of the solid-gas reaction of biCl3 to biOCl via the intermediate hydrate biCl3·H2O
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At ambient conditions the hydrolysis of BiCl3 to BiOCl proceeds via the intermediate hydrate: BiCl3-H2O as has been revealed by fimo dependent in-situ X-ray powdor diffraclion as well as time; and temperature controlled TG-MS experiments. Below 50 °C the topochemical formation of the hydrate can be reversed by reduciny the H2O vapour pressure. Above this temperature the hydrate is unstable and the mechanism of the hydrolysis changes. BiCl3·H2O crystallizes in the monoclinic space group C2/m with lattice parameters a = 1114.25(1) pm, b = 876.82(1) pm, C = 584.20(1) pm, and β = 106.64(1)°.
- Wosylus, Aron,Hoffmann, Stefan,Schmidt, Marcus,Ruck, Michael
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- Constitutional isomerism of BiW6Cl15: (BiCl)[W 6Cl14] and (BiCl2)[W6Cl 13]
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The compound (BiCl)[W6Cl14] was previously characterized as a product of the reduction of tungsten hexachloride with elemental bismuth. Another modification of BiW6Cl15 is now presented as (BiCl2)[Ws
- Stroebele, Markus,Meyer, H.-Juergen
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- Reactions of Chlorine with Liquid Metals. 3. Bismuth
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The reaction of molecular chlorine with solid and liquid bismuth was studied by modulated molecular beam-mass spectrometric methods over temperature range 400-800 K and equivalent chlorine pressures of 5 * 10-6-2 * 10-4 torr.The sole reaction product with solid Bi(0001) was BiCl3.This species disappeared at the melting point.The molecular beam data collected on the trichloride product exhibited nonlinearity and evidence of both branched and series processes in the mechanism.These results, in conjunction with data obtained in a prior investigation of the system by thermal desorption spectroscopy, permitted development of a model of the reaction on the surface of the solid.With liquid bismuth, only BiCl was detected as reaction product.Its reaction probability increased with temperature, most likely because of a corresponding increase in the chlorine sticking probability.The 45 deg phase lag exhibited by this species indicated that the kinetics were dominated by solution and diffusion of chlorine in the bulk liquid bismuth.
- Balooch, M.,Siekhaus, W. J.,Olander, D. R.
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- Investigations on the pseudobinary system Bi2Se3/BiCl3
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The phase diagram of the pseudobinary system Bi2Se3/BiCl3 was investigated by DTA, total pressure measurements and x-ray phase analysis. The two ternary phases BiSeCl and Bi8Se9Cl6 melt inc
- Petasch,Oppermann
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- Syntheses, properties and crystal structures of the cluster salts Bi 6[PtBi6Cl12] and Bi2/3[PtBi 6Cl12]
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Melting reactions of Bi with Pt and BiCl3 yield shiny black, air insensitive crystals of the subchlorides Bi6[PtBi6Cl 12] and Bi2/3[PtBi6Cl12]. Despite the substantial difference in the bismuth content the two compounds have almost the same pseudo-cubic unit cell and follow the structural principle of a CsCl type cluster salt. Bi6[PtBi6Cl12] consists of cuboctahedral [PtBi6Cl12]2- clusters and Bi62+ polycations (a = 9.052(2) A, α = 89.88(2)°, space group P1, multiple twins). In the electron precise cluster anion, the Pt atom (18 electron count) centers an octahedron of Bi atoms whose edges are bridged by chlorine atoms. The Bi62+ cation, a nido cluster with 16 skeletal electrons, has the shape of a distorted octahedron with an opened edge. In Bi2/3[PtBi6Cl12] the anion charge is compensated by weakly coordinating Bi3+ cations which are distributed statistically over two crystallographic positions (a = 9.048(2) A, α = 90.44(3)°, space group R3). Bi 6[PtBi6Cl12] is a semiconductor with a band gap of about 0.1 eV. The compound is diamagnetic at room temperature though a small paramagnetic contribution appears towards lower temperature.
- Hampel, Silke,Ruck, Michael
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- Solution-phase template approach for the synthesis of Cu2S nanoribbons
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In this paper, we have developed a solution-phase template approach to synthesize Cu2S nanoribbons for the first time. Bi2S 3 nanoribbons act as both template and reactant when treated with small CuCl particles, generating Cu2S nanoribbons with the assistance of the solvent ethanol. Nanoribbons with different compositions of Bi 2S3 and Cu2S also could be obtained through controlling the reaction time. This kind of template method is expected to be a general template approach due to its slow reaction rate and simplicity. The Royal Society of Chemistry 2006.
- Li, Zhengquan,Yang, Huan,Ding, Yue,Xiong, Yujie,Xie, Yi
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- Synthesis, structure and properties of the first hybrid Bi 2Cl93- supramolecular compound based on macrocyclic rotator-stator assembly
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The first hybrid Bi(III) supramolecular compound based on organic ammonium and 18-crown-6, [(4-FBNH3)3·(18-crown-6) 3·(Bi2Cl9)] (1), has been synthesized and characterized by single crystal X-ray diffraction, elemental analysis, IR, XRPD and 1H NMR (4-FBNH3 = 4-fluorobenzenaminium). The Bi(III) centers were chelated through three μ2-Cl donors to form a macro-anion (Bi2Cl9)3- unit. And the rotator-stator assembly, [(4-FBNH3)·(18-crown-6)]+, was formed by the 4-FBNH3+ cation inserting into the crown ether through strong NH...O H-bonding interactions. The large anions and rotator-stator cations were alternately stacked together to build the supramolecular functional compound. In addition, the thermal analysis and luminescent properties were investigated.
- Peng, Yan-Hong,Sun, Shao-Fa
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- Facile reduction of early transition metal halides with nonconventional, mild reductants (see abstract)
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Reduction of MoCl5 with Bi in a sealed borosilicate ampule at 350°C, followed by sublimation of by-product BiCl3 and addition of aqueous hydrochloric acid, yielded chloromolybdic acid, (H3O) 2Mo6(μ3-Cl)8Cl 6·6H2O, in 80% yield (unoptimized) after double recrystallization. Chloromolybdic acid was thermolyzed to Mo6Cl 12 in 95% yield.
- Hay, Daniel N.T.,Adams, Juan A.,Carpenter, Jason,DeVries, Stephanie L.,Domyancich, John,Dumser, Bruce,Goldsmith, Shawn,Kruse, Melissa A.,Leone, Angela,Moussavi-Harami, Farid,O'Brien, Jennifer A.,Pfaffly, Jennifer R.,Sylves, Michael,Taravati, Parisa,Thomas, Jacob L.,Tiernan, Breck,Messerle, Louis
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- The bicyclic polyselenium cation Se102+ in the structure of Se10[Bi4Cl14]
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In the ternary system Se/Bi/Cl a new polycation containing phase besides the already known Se4[Bi4Cl14], Se 8[Bi4Cl14], and Se10[Bi 5Cl17] was discovered. Red, transparent, plate shaped crystals of Se10[Bi4Cl14] were formed by reaction of Se/SeCl4/BiCl3 in 15:1:8 molar ratio in evacuated glass ampoules applying a temperature gradient from 90 to 80 °C. The crystal structure consists of bicyclic Se102+ cations and of layered chloridobismutate anions with the cations located between the anionic planes. The atoms of the cation form a six membered ring with a Se 4 chain bridging over the 1,4 positions of the Se6 ring. The anions are made up of BiCl7 polyhedra connected by common edges to layers 2∞[Bi4Cl14 2-]. Se4[Bi4Cl14], Se 8[Bi4Cl14], Se10[Bi 4Cl14], and Te8[Bi4Cl14] all contain an anion of identical formula and two-dimensional connectivity, but these polymeric chlorido-bismutates are not isostructural. The structural differences are discussed on basis of the different topologies of the nets made up by the bismuth atoms.
- Beck, Johannes,Eck, Steffen J.
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p. 1910 - 1912
(2011/01/05)
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- Crystalline and glassy phases in the ternary system Tl/Bi/Cl: Synthesis and crystal structures of the thallium(I) chloridobismutates(III) Tl3BiCl 6 and TlBi2Cl7
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Slow cooling of melts composed of TlCl and BiCl3 allows for the isolation of the compounds Tl3BiCl6 (1) and TlBi 2Cl7 (2). Compound 1 is formed by sublimation at 480 °C from the black melt of 3 TlCl + 1 BiCl3 as colourless crystals. The crystal structure determination (tetragonal, P42/m) consists of nearly regular octahedral [BiCl6]3- anions and two independent Tl+ cations, which have coordination number 8 in form of a slightly distorted cube and 10 in form of an Edshamar polyhedron, respectively. The structure is not isotypic with the recently reported naturally occurring form of Tl3BiCl6, the mineral steropesite. Compound 2 is obtained from a dark red melt of composition TlCl + 2 BiCl 3. On rapid cooling, this melt solidifies to a metasta-ble dark red glass which at ambient temperature crystallises to a light amber crystalline powder within some weeks. The structure of 2 was determined by powder diffraction (triclinic, P1). A distinct lone pair effect is present causing an irregular coordination on the two independent bismuth atoms. Taking Bi-Cl bonds up to 3.5 A into account, both bismuth atoms gain coordination number seven. 203T1 and 205Tl solid state NMR and XANES spectra on the Bi and Tl-LIII edges of both glassy and crystalline TlBi2Cl7 show that a close structural similarity exists between both forms. In contrast, the Raman spectra show distinct differences in the bands of the Bi-Cl vibrations region.
- Beck, Johannes,Benz, Sebastian
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p. 928 - 935
(2010/09/10)
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- Phase diagrams of some non-quasi-binary joins of the AlCl 3-BiCl3-NaCl system
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Phase diagrams of NaAlCl4-(70.0 mol % AlCl3 + 30.0 mol % BziCl3), NaAlCl4-(34.2 mol % AlCl3 + 65.8 mol % BiCl3), and (61.0 mol % AlCl3 + 39.0 mol % NaCl)-AlCl3 ? BiCl
- Kaloev,Turieva
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p. 312 - 314
(2009/08/14)
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- Precipitation of bismuth(III) salicylates from mineral acid solutions
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Powder X-ray diffraction, IR spectroscopy, Raman spectroscopy, thermogravimetry, and chemical analysis were used to study the precipitation of bismuth(III) salicylates from perchloric, nitric, and hydrochloric acid solutions as dependent on the salicylate
- Timakova,Udalova,Yukhin
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p. 873 - 880
(2009/10/01)
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- Reaction of a mixture of bismuth and iron oxides with chlorine and sulfur dioxide
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The processes in a heterogenous multicomponent system Bi2O 3-Fe2O3-Cl2-SO2. are explored. In the temperature range 300-700°C is clearly developed mutual influence of chemical reactions at introducing to the system of an additional component: chloridosublimation of both bismuth and iron in the presence of SO2 and chloridosublimation of bismuth at adding iron oxide to bismuth oxide are accelerated. In the region of the higher temperatures the possible chemical reactions in the system proceed independently: SO2 only dilutes chlorine and mutual influence of bismuth and iron oxides is not found.
- Derlyukova,Vinokurova
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p. 1836 - 1842
(2009/02/08)
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- Effect of SO2 on chlorination of Bi2O3 + Fe2O3 mixtures
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The reaction of Bi2O3 + Fe2O3 mixtures with chlorine and SO2 at 250-700°C is studied. At 300-500°C, the degree of bismuth chloride sublimation from the oxide mixture increases in the presence of SOsu
- Derlyukova,Vinokurova,Anufrieva
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p. 1371 - 1375
(2009/05/06)
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- Compositional modification of bismuth-containing nanoparticles in a polyethylene matrix
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A method was developed for manufacturing isolated bismuth(III)-containing (oxide, chloride, or oxochloride) nanoparticles by the thermodestruction of proper salts in a solution-melt of low-density polyethylene (LDPE) in an oil. The size and composition of the nanoparticles were determined by transmission electron microscopy and X-ray powder diffraction. Well-known reactions (with KOH, O2, H2O2, and C12) and the reactions of isopropanol in a supercritical fluid (SCF) state with the bismuth-containing nanoparticles were used to prove the feasibility of modifying the composition of the nanoparticles stabilized in the bulk of the polyethylene matrix. The nanoparticles stabilized in this manner retain their chemical activity, thus allowing their composition to be modified.
- Yurkov,Astafiev,Gorkovenko,Buslaeva,Kargin,Gubin
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p. 1300 - 1305
(2008/10/09)
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- Investigations on the pseudobinary system Bi2Te3/BiCl3
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The phase diagram of the pseudobinary sytem Bi2Te3/BiCl3 was investigated by DTA, total pressure measurements, and X-ray phase analysis. Only BiTeCl exists as a ternary phase in this system. The compound melts incongruently at 430 °C. The heat of formation and the standard entropy of BiTeCl were calculated from vapor pressure data: ΔH°B (BiTeCl, f, 298) = (-39,5 ± 1,6) kcal/mol; S° (BiTeCl, f, 298) = (34,4 ± 2,7) cal/K-mol. The heat of formation of BiCl3 was determined on the basis of the heat of solution of BiCl3 and Bi2O3, and the heat of formation of Bi2O3: ΔH°B (BiCl3, f, 298) = (-95,9 ± 0,9) kcal/mol.
- Petasch,Hennig,Oppermann
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p. 234 - 238
(2007/10/03)
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- Lewis-acid-base-reactions of gold trihalides with bismuth trihalides - Synthesis and structures of AuBiX6 (X = Cl, Br)
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Gold trihalides AuX3 (X = Cl, Br) react with bismuth trihalides in sealed glass ampoules to the 1:1 adducts AuBiX6 (X = Cl, Br). AuBiCl6 is obtained by a chemical transport reaction at 220 °C, whereas AuBiBr6 was synthesized by solvothermal reaction in SiBr4 at 1.50 °C. Both compounds crystallize triclinic, space group P1?, Z = 4, AuBiCl6: a = 698.3(4) pm; b = 1009.3(5) pm; c = 1381(1) pm; α = 104.98(5)○; β = 94.73(5)○; γ = 110.06(3)○; V = 867(1) · 106 pm3. AuBiBr6: a = 735.7(4) pm; b = 1055.7(5) pm; c = 1445(1) pm; α = 104.88(5)○; β = 94.25(5)○; γ = 110.18(4)○; V = 1001(1) · 106 pm3. The structures are build formally of square-planar [AuX4]- and chains of edge-connected ([BiX4/2]+)n units. Since each Bi ion is surrounded by eight halogenide ions in a square-antiprismatic form, the structure can alternatively be described as consisting of chains of edge sharing ([BiX4X4/2]3-)n antiprisms connected by Au3+ ions.
- Beck,Wagner
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p. 1810 - 1814
(2008/10/09)
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- Bi11Se12Cl9: Synthesis and Crystal Structure
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The Bi11Se12Cl9 phase (I), previously known as BiSeCl, is synthesized by the ampule technique. The X-ray crystal structure of I is determined (space group Cm, a = 36.444(5) ?, b = 4.0844(6) ?, c = 12.073(2) ?, β = 91.16(1)○, Z = 2). The structure of I consists of alternating ∞1[BiSe] double zigzag chains. Bismuth atoms are hexa- and heptacoordinated with selenium and chlorine atoms. Similarities and dissimilarities between crystal structures of I and SbSBr are discussed. It is shown that compounds AVBVICVII, regardless of their specific crystal structure, are characterized by covalent metal-chalcogen bonds and mainly ionic metalhalogen bonds.
- Trifonov,Shevel'kov,Dikarev,Popovkin
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p. 1117 - 1120
(2008/10/08)
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- Properties and reactions of tris(2,6-difluorophenyl)bismuth(III) and tris(2,6-difluorophenyl)bismuth(V) derivatives
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(2,6-F2C6H3)3BiF2 and (2,6-F2C6H3)3BiCl2 are prepared oxidizing (2,6-F2C6H3)3Bi with XeF2
- Lewe,Naumann,Nowicki,Schneider,Tyrra
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p. 122 - 128
(2008/10/09)
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- Reactivity of Sulphuryl Chloride in Acetonitrile with the Elements
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Sulphuryl chloride in MeCN reacts with all but the most refractory elements to give mainly solvated chlorides at or below 300 K in contrast with SO2Cl2 alone which requires at least twice this temperature.There is evidence for an ionic mechanism based on analogy, thermochemistry, transport measurements and additive effects.The instability of these solutions leading to polymerization, together with its inhibition, is described.Sulphur dioxide formed in reactions seldom plays a reductive role apart from influencing formation of the mixed-valence Tl4Cl6.Semiquantitative kinetic measurements in different solvents emphasize the uniqueness of MeCN.For most elements attack is diffusion controlled across surface films giving a parabolic dependence on time which can be linearized if film growth is prevented by changing the solvent mix.The varied nature of these surface films vitiates any simple relation between rate and periodicity.Some applications are indicated.
- Woolf, Alfred A.
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p. 3325 - 3330
(2007/10/02)
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- Catalysis, by nitrogen oxides, of oxidation of bismuth sulfide by oxygen
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By means of potentiometric and atomic absorption analysis of the solution and IR spectroscopy of the gas phase, a kinetic study has been made of the topochemical oxidation of bismuth sulfide in solution in the presence of nitrogen oxides. Equations describing the experimental results are presented. The quantum-chemical characteristics of the species participating in catalysis have been calculated by CNDO method.
- Kogan,Emel'yanova,Serdyukova,Dorfman,Doroshkevich
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p. 964 - 969
(2008/10/08)
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- SYNTHESIS AND REACTIONS OF MIXED HALIDE DIALKYLDITHIOPHOSPHATE DERIVATIVES OF BISMUTH(III)
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Mixed chloride dialkyldithiophosphates of bismuth(III), nBiCl3-n (n = 1,2; R = Et, Prn, Pri and Bui) have been synthesized for the first time by the reactions of bismuth trichloride with sodium diisopropyldithiophosphate or alternatively by co-disproportionation reactions of bismuth trichloride with bismuth tris(dialkyldithiophosphates) in different stoichiometric ratios in suitable organic solvents.Monohalobismuth bis(diisopropyldithiophosphates) have also been synthesized by the cleavage reactions of bismuth tris(dialkyldithiophosphates) with bromine or iodine in 2:1 molar ratio.These new derivatives have been characterized by elemental analysis, molecular weight determinations (both cryoscopic and ebullioscopic) as well as spectroscopic (IR, 1H NMR and 31P NMR) studies.On the basis of these data chelated structures with bidentate dialkyldithiophosphate groups have been proposed for these monomeric derivatives.Hydrolysis reactions of some of these compounds have also been studied.
- Chauhan, H. P. S.,Srivastava, G.,Mehrotra, R. C.
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p. 161 - 168
(2007/10/02)
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