- 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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- Preparation, vibrational spectra, and crystal structure of dithionitronium hexachloroantimonate(V), (S2N)(SbCl6)
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Dithionitronium hexachloroantimonate(V), (S2N)(SbCl6), has been prepared by the reactions of S7NH, S7NBCl2, and 1,4-S6N2H2 with SbCl5 in liquid SO2. The structure of the compound has been determined by single-crystal X-ray diffraction. The orthorhombic crystal, space group I222, has cell dimensions a = 9.299 (3) ?, b = 7.976 (3) ?, and c = 7.070 (2) ? and has two formula units in the unit cell. Intensities were measured using Mo Ka radiation and a Syntex P21 diffractometer. The crystal structure was determined by standard methods and refined to R1 - 0.0377, R2 = 0.0375. The crystal is composed of linear S2N+ cations (N-S = 1.464 (3) ?) and approximately octahedral SbCl6- anions (Sb-Cl = 2.351 (3), 2.363 (2) ?). Infrared and Raman spectra of the solid compound are reported.
- Faggiani, Romolo,Gillespie, Ronald J.,Lock, Colin J. L.,Tyrer, J. David
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- Reversible Isomerization of Cyclo-octasulfur Monoxide; Preparation and X-Ray Crystal Structure of S8O*SbCl5
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The reaction of S8O and SbCl5 in CS2 gave S8O*SbCl5 (71percent yield) which was shown by X-ray crystallography to contain S8O in an isomeric conformation compared with pure S8O which can be recovered from the adduct in its usual conformation by recrystall
- Steudel, Ralf,Sandow, Torsten,Steidel, Juergen
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- Synthesis, Isolation and Structures of Trifluoromethylated Fullerenes D2-C76, C76(1)(CF3)10–18
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High-temperature trifluoromethylation of fullerene C76 chlorination products followed by HPLC separation of C76(CF3)n derivatives resulted in the isolation and X-ray structural characterization of thirteen Csub
- Tamm, Nadezhda B.,Ignat'eva, Daria V.,Aslanov, Leonid A.,Troyanov, Sergey I.
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- Luminescent properties of Bi3+-activated Ca2Sb2O7 nano-phosphor prepared by co-precipitation method
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A series of Ca2Sb2O7:xBi3+ (x = 0, 0.5, 1, 1.5, 2, 4 and 8 mol%) blue phosphors were synthesized using a chemical co-precipitation technique with further calcination. The X-ray diffraction (XRD) and scanning electron microscope (SEM) results revealed that the obtained Ca2Sb2O7:xBi samples are orthorhombic weberite structure with particle size ranging from 20 nm to 40 nm. X-ray photoelectron spectroscopy (XPS) confirmed that the introduction of bismuth into the Ca2Sb2O7 crystal was in the form of Bi3+ and no other chemical states were found. The Bi-doped Ca2Sb2O7 powders exhibit a broad emission band centered at 438 nm upon UV-irradiation and it is characterized by double-luminescence centers. The dependence of the luminescent intensity on the Bi-doping concentration in Ca2Sb2O7 was studied in detail. As a result, the optimized concentration of Bi3+ is 1.5 mol% for the highest emission intensity peaking at 438 nm, and the concentration quenching occurs when the concentration of Bi3+ exceeds 1.5 mol%. The luminescence mechanism of Bi3+ in Ca2Sb2O7 was also discussed. The favorable luminescent properties of Ca2Sb2O7:Bi3+ make it promising for lighting and display applications.
- Yao, Shiyue,Zhou, Xuan,Huang, Yanling,Wang, Zuoshan,Long, Yumei,Li, Weifeng
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- Reaction of C60 with SbCl5
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C60 was doped with SbCl5 by the direct reaction with liquid SbCl5 or with SbCl5 dissolved in CCl4. Mass spectrometer analysis showed that the compound consisted of Cl2, SbCl3 and C60. The SbCl5 was removed by sublimation leaving Cl2 in C60. The doped compound was electrically conducting at room temperature. The resistivity increased with decreasing temperature corresponding to a semiconducting energy gap of 1.1 eV.
- Daters, W. R.,Ummat, P. K.,Olech, T.,Nkum, R. K.
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- Lead-Free Hybrid Material with an Exceptional Dielectric Phase Transition Induced by a Chair-to-Boat Conformation Change of the Organic Cation
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Hybrid organic-inorganic perovskite materials have demonstrated great potential in the field of photovoltaics and photoelectronics. On the basis of the high degree of structural flexibility and compatibility, diverse molecular functional materials have been assembled by modifying the length of the organic components and/or dimensionality of the inorganic frameworks. In this paper, we present a chiral lead-free organic-inorganic hybrid, (piperidinium)2SbCl5 (1), which follows the one-dimensional inorganic frameworks of the corner-sharing SbCl6 octahedra. Strikingly, 1 displays a dielectric phase transition at Tc = 338 K, changing from the chiral space group of P212121 to polar Pna21 upon heating. Crystal structure analyses reveal that an unusual thermally activated conformation change of the piperidinium cations affords the driving force to the phase transition of 1. That is, organic piperidinium moieties display a chairlike conformation below Tc, which transforms to a boatlike structure above Tc. Such an unprecedented change is strongly coupled to the dielectric transition along with notable steplike anomalies, which suggest that 1 could be used as a potential switchable dielectric material. Besides, the temperature-dependent conductivity and theoretical analysis of its electronic structure disclose the semiconducting behavior of 1. This study paves the pathway to the design of new lead-free semiconducting perovskites with targeted properties for optoelectronic application.
- Han, Shiguo,Zhang, Jing,Sun, Zhihua,Ji, Chengmin,Zhang, Weichuan,Wang, Yuyin,Tao, Kewen,Teng, Bing,Luo, Junhua
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- Sandwich-Type Uranyl Phosphate-Polyoxometalate Cluster Exhibiting Strong Luminescence
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A pure inorganic uranyl phosphate-polyoxometalate of Na17{Na@[(SbW9O33)2(UO2)6(PO3OH)6]}·xH2O (abbreviated as Na@U6P6, with x ≈ 46) featuring a sandwich-type structure was prepared using Keggin-type trilacunary [α-B-SbW9O33]9- units as building blocks, which were formed in situ by SbCl3 and Na2WO4·2H2O. Crystal structural analysis showed that six UO22+ cations and six PO3OH2- anions generated a wheel-like cluster unit with a Na+ center ([Na@(UO2)6(PO3OH)6]+) that is stabilized by two [α-B-SbW9O33]9- units. Na@U6P6 displayed a solid-state photoluminescence quantum yield of 33% at 300 K. The temperature-dependent fluorescence emission spectra showed that Na@U6P6 has temperature-sensitive fluorescence in which its emission intensity decreased by 77% as the temperature increased from 200 to 300 K. These results suggest that such uranyl phosphate-polyoxometalate clusters could serve as potential temperature-sensitive molecular materials.
- Kong, Xiang-Jian,Long, La-Sheng,Wang, Hai-Ying,Zheng, Lan-Sun,Zheng, Xiu-Ying
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- Thermal decomposition of antimony oxyhalides. I. Oxychlorides
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The thermal decomposition of SbOCl, Sb4O5Cl2 and Sb8O11Cl2 has been studied by thermogravimetry with identification of the products resulting in the condensed phase by X-ray diffraction and
- Costa, L.,Paganetto, G.,Bertelli, G.,Camino, G.
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- Unexpected product formed by the reaction of [2,6-(MeOCH2)2C6H3]Li with SbCl3: Structure of Sb-O intramolecularly coordinated organoantimony cation
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Reaction of [2,6-(MeOCH2)2C6H3]Li (1) with SbCl3 in 1:1 molar ratio yielded except the intended product [2,6-(MeOCH2)2C6H3]SbCl2 (2) unexpected c
- Dostál, Libor,Jambor, Roman,Císa?ová, Ivana,Bene?, Ludvík,R??i?ka, Ale?,Jirásko, Robert,Hole?ek, Jaroslav
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- Ferrocene linked to PtL2 fragments (L2 = Cl 2, fumaronitrile, 3,6-Di-tert-butylcatecholato): A spectroscopic and theoretical investigation of redox behavior and charge distributions
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The optical and redox properties of a ferrocene-appended diimine ligand (1) and its PtL2 complexes [L2 = Cl2 (2), fumaronitrile (3), 3,6-di-tert-butylcatecholato (4)] are reported. The chromophores are characterized by NMR, UV/vis, and IR spectroscopy as well as cyclic voltammetry. Preparative oxidations to radical cations using Magic Blue [N(p-C6H4Br)3][SbCl6] or silver triflate in conjunction with UV/vis, NMR, and EPR spectroscopy were used to probe the chloride-dependent redox chemistry of ligand 1 and platinum complexes 2-4. Density functional calculations were employed to corroborate geometric and electronic descriptions of 1-4 and their oxidized counterparts.
- Heinze, Katja,Reinhardt, Sven
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p. 5406 - 5414
(2008/10/09)
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- Chlorination of C60 and C70 fullerenes using SbCl5 and VCl4 chlorides
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Fullerenes C60 and C70 are reacted with variable-valence element chlorides (SbCl5 or VCl4) in glass ampoules at 160-180°C to yield chlorides C60Cl24 and C70Cl28, respectively. The products are characterized using elemental analysis, IR spectroscopy, and thermal analysis. The use of C60Br24 or C70Br10 instead of C 60 or C70 in the reactions with SbCl5 substantially shortens the reaction time. It is for the first time that a high degree of chlorination (C70Cl28) of fullerene C 70 against the literature data (C70Cl10) has been achieved.
- Troyanov,Shustova,Popov,Feist,Kemnitz
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p. 1303 - 1307
(2008/10/09)
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- [{ReN(Me2PhP)(Et2dtc)Cl}2{ReN(Et 2dtc)2}2{SbCl3}2] - A novel tetranuclear rhenium complex with asymmetric nitrido bridges
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The reaction of [ReN(Et2dtc)2(Me2PhP)] (Me2PhP = dimethylphenylphosphine, Et2dtc- = diethyldithiocarbamate) with SbCl3 in dichloromethane results in the formation of [{ReN(Me2PhP)(Et2dtc)Cl}2{ReN(Et 2dtc)2}2{SbCl3}2]. A {Re≡N-}4 ring with asymmetric nitrido bridges is stabilised by the co-ordination of SbCl3 onto the chloro ligands and sulphur atoms of the dithiocarbamates. The compound decomposes upon heating in acetonitrile and the fragments of the tetrameric complex re-arrange to form [ReN(Me2PhP)(Et2dtc)Cl]4 and [ReN(Et2dtc)2]. The multinuclear rhenium compounds have been studied by X-ray crystallography. The 8-membered {Re≡N-}4 ring system in [{ReN(Me2PhP)(Et2dtc)Cl}2{ReN(Et 2dtc)2}2{SbCl3}2] is almost planar, while that of [ReN(Me2PhP)(Et2dtc)Cl]4 is clearly V-shaped when viewed down either diagonal Re...Re axis. A dihedral angle of 47.88(2)° has been found between the contributing planes.
- Stelzer,Hagenbach,Abram
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p. 703 - 706
(2008/10/08)
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- Synthesis and study of mixed tin and antimony oxides
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Coprecipitation of tin(II, IV) and antimony(III) from chloride solutions was studied by X-ray phase analysis, thermogravimetry, IR spectroscopy, and elemental analysis.
- Arapnev, A. I.,Yukhin, Yu. M.,Malinovskaya, T. D.,Egorov, Yu. P.
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p. 1557 - 1561
(2008/10/08)
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- Silyl-nitrogen compounds: Part XIII - Reactions of metal halides with silylated tosylhydrazines
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Bis(trimethylsilyl)tosylhydrazine (Me3Si)2TsN2H reacts with ECln (E=Al,Sn,Sb or Ti) to liberate Me3SiCl and in the process form tosylhydrazides, ECln·1(Me3Si)TsN2H. These compounds decompose on heating in vacuo to form a variety of azane derivatives with the loss of volatile products like Me3SiCl, HCl or SbCl3. Ditosyltetrazene intermediate decomposes into ditosylhydrazine whose structure is determined by X-ray diffraction.
- Vasisht,Venugopalan,Kataria, Jyoti,Sharma, Anuradha
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p. 2054 - 2059
(2007/10/03)
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- Sb2SmO4Cl, the first antimony rare-earth oxide chloride
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The new quaternary phase Sb2SmO4 Cl was prepared by solid-state reaction of a stoichiometric mixture of SbCl3, Sb2O3, and Sm2O3. Sb2SmO4Cl is the first antimony rare-earth oxide chloride. It was characterized by X-ray powder diffraction, IR-spectroscopy, mass spectrometry and DTA/TG measurements. The standardenthalpy of formation was derived from heats of solution. The standard entropy were calculated from a low-temperature measurement of the specific heat capacity. WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001.
- Schmidt, Marcus
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p. 2105 - 2111
(2008/10/08)
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Various mesityl, alkoxy and aryloxy-stibanes were prepared from the corresponding mesitylchlorostibanes. The reaction of the same mesitylchlorostibanes with the 3,5-di-t-butyl catechol first leads to the formation of a Sb V complex observed by 1H NMR. Depending on the experimental conditions the reaction can fork from this intermediate. Intramolecular hydrochloride elimination when this is trapped using a tertiary amine, leads to 2-mesityl-1,3-dioxa-4,6-di-t-butylbenzo-2-stibolane while the absence of a tertiary amine allows an acidic cleavage of the mesityl-antimony bond with formation of 2-chloro-1,3-dioxa-4,6-di-t-butylbenzo-2-stibolane.
- Benmaarouf,Riviere,Riviere-Baudet,Castel,Khallaayoun,Ahbala
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- THE LOWER OXIDES OF SULFUR AND RELATED ORGANIC SULFOXIDES
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The preparation, structures, spectra and other properties of organic sulfane oxides, R2SnO (n = 3,4), and dioxides, R2SnO2 (n = 3,4), as well as of the homocyclic sulfur oxides SnO (n=6...10) and SnO2 (n = 7,12) are discussed.All compounds are sulfoxides and contain two or more homonuclear S-S bonds.
- Steudel, Ralf
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- SOME CO-ORDINATION COMPOUNDS OF TaCl3S AND TaBr3S. X-RAY CRYSTAL STRUCTURE OF
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The reaction of TaX5 (X = Br or Cl) with Sb2S3 (molar ratio 3:1) led to the formation of TaX3S.With L these species form complexes of formulation TaX3S*2L (L = dimethyl sulphide, tetrahydrothiophene, or MeCN) and TaX3S*L .The exact nature of the complexes was ascertained by a single-crystal X-ray study on TaCl3S*bpte.The crystals are monoclinic, space group P21/c, Z = 4 with a = 15.538(20), b = 7.352(8), c = 16.619(20) Angstroem, and β = 110.88(10) deg. 2 003 Independent reflections with I>4?(I) were used in the refinement and a R value of 0.062 obtained.The structural study showed that the metal atom was in a distorted octahedral environment with a terminal Ta=S bond , three metal-chlorine interactions , and two bonds to the sulphur atoms of the ligand.The bond trans to the terminal sulphur atom is longer than the bond that is cis .The Ta=S fragment has the expected influence on the three angles it forms at the metal with the three chlorine atoms that are bound cis to it, increasing the angles to ca. 100 deg.This is concomitant with a surprisingly small value of 86.5(2) deg for the angle S=Ta-S(cis).
- Drew, Michael G. B.,Rice, David A.,Williams, David M.
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p. 845 - 848
(2007/10/02)
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- Interhalogen Cations: Preparation and Crystal Structures (143 K) of I3Cl2SbCl6, I3Cl2AlCl4 and I3Br2SbCl6
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The title compounds were prepared and their crystal structures determined from low temperature single crystal X-ray data.The structures contain the anions SbCl6(-) and AlCl4(-) and the novel interhalogen cations I3Cl2(+) and I3Br2(+).Anions and cations ar
- Pohl, Siegfried,Saak, Wolfgang
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p. 283 - 288
(2007/10/02)
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- Preparation, X-ray crystal structures, and vibrational spectra of some salts of the As3S4+ and As3Se4+ cations
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The reactions of α- and β-As4S4 and some arsenic-selenium melts with various oxidants in SO2 as solvent are reported. It is shown by X-ray crystallography that the reactions of As4S4 and a 1:1 As-Se melt with the Lewis acids AsF5 and SbF5 in a 1:3 molar ratio in SO2 give the hexafluoroarsenate and hexafluoroantimonate salts of the novel arsenic chalcogen cations As3S4+ and As3Se4+. Crystals of (As3S4)(SbF6) are yellow plates which crystallize in the orthorhombic space group Pcam with a = 20.453 (4) A?, b = 5.990 (1) A?, c = 9.609 (2) A?, U = 1177.3 (4) A?3, and dc = 3.32 g cm-3 for Z = 4. Crystals of the isomorphous (As3S4)(AsF6) are dark yellow prisms and rhombs with cell dimensions a = 19.962 (4) A?, b = 5.930 (1) A?, c - 9.441 (3) A?, U = 1115.8 (5) A?3, and dc = 3.22 g cm-3 for Z = 4. The compound (As3Se4)(SbF6) forms orange diamond-shaped plates which crystallize in the monoclinic space group P21/m with a = 6.224 (3) A?, b = 9.564 (5) A?, c = 10.643 (5) A?, β = 92.65 (4)°, U = 632.9 (5) A?3, and dc = 4.07 g cm-3 for Z = 2. The structure of the compound (As3S4)(SbF6) was solved by using the Patterson function and refined by least-squares methods to final agreement indices R1 = 0.036 and R2 = 0.043 for 699 observed data. The isomorphous compound (As3S4)(AsF6) has similarly been refined by least-squares methods to final agreement indices R1 = 0.043 and R2 = 0.052 for 546 observed data. The structure of the compound (As3Se4)(SbF6) was solved by using direct methods and has been refined by least-squares to final agreement indices R1 = 0.064 and R2 = 0.082 for 620 observed reflections. The two cations As3S4+ and As3Se4+ are isostructural with crystallographic mirror symmetry and an overall symmetry of Cs. The cage structure of the two cations can be derived by bridging three edges of a tetrahedron of three arsenic and one sulfur or selenium atoms by the remaining sulfur or selenium atoms. Bond distances, bond angles and some significant interionic contact distances in these compounds are discussed. In addition, the Raman and IR spectra of these cations as well as the Raman spectrum of As4S3 and an improved Raman spectrum of the compound α-As4S4 are reported.
- Christian, Beverley H.,Gillespie, Ronald J.,Sawyer, Jeffery F.
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p. 3410 - 3420
(2008/10/08)
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