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1.
Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O], and (PPh4)2[SnCl6] · S8 · 2CH3CN . The reaction of PPh4[SnCl3] with Na2S4 in acetonitrile in the presence of small amounts of water yields (PPh4)2[Sn4Cl4S5(S3)O] and minor amounts of (PPh4)2[SnCl2(S6)2], PPh4Cl · 2S8 and (PPh4)2[SnCl6]. SnCl4 is partially reduced by (PPh4)2Sx, PPh4[SnCl3] and (PPh4)2[SnCl6] · S8 · 2CH3CN being produced. According to the X-ray crystal structure determination the [Sn4Cl4S5(S3)O]2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S3 group. In the [SnCl2(S6)2]2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S6 groups. Octahedral [SnCl6]2? ions and S8 molecules in the crown conformation are present in (PPh4)4[SnCl6] · S8 · 2CH3CN.  相似文献   

2.
Pentabromothio-diarsenate and -diantimonate: Preparation, Vibrational Spectra, and Crystal Structures of PPh4[As2SBr5] and PPh4[Sb2SBr5] The title compounds were obtained in CH2Br2 from PPh4Br, HBr and As2S3 or Sb2S3, respectively. Their i.r. and Raman spectra are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh4[As2SBr5], monoclinic, space group P21/n, Z = 4, a = 1192.3, b = 1528.1, c = 1618.0 pm, β = 95.53°, isotypic with PPh4[As2SCl5] (structure determination with 1539 observed reflexions, R = 0.052); PPh4[Sb2SBr5], triclinic, space group P1 , Z = 2, a = 1044,8, b = 1207.1, c = 1307.8 pm, α = 104.77, β = 108.63, γ = 98.34° (2398 observed reflexions, R = 0.032). Both ions, [As2SBr5]? and [Sb2SBr5]?, have the same general structure: including the lone electron pairs, the As and Sb atoms have distorted trigonal-bipyrimidal coordination, two bipyramids sharing a common edge with sulfur and bromine as bridging atoms. The [As2SBr5]? ions are associated to chains via As…Br contacts, the [Sb2SBr5]? ions form pseudodimeric units by Sb…S and Sb…Br contacts. Whereas the crystal packing of the As compound is similar to that of other PPh4+ compounds having a cation to anion ratio of 1:1, the Sb compound shows the packing principle known for 2:1 compounds.  相似文献   

3.
(PPh4)2[OsCl3(NO) (SnCl3)2]; Preparation, I.R. Spectrum, and Crystal Structure (P(C6H5)4)2[OsCl3(NO)(SnCl3)2] yields from the reaction of OsCl3(NO) with PPh4-[SnCl3] in dichloro methane forming red crystals. The complex crystallizes monoclinic in the space group C2/c with four formula units per unit cell. The crystal structure was determined by aid of X-ray diffraction data (2261 independent, observed reflexions, R = 4.9%). The cell parameters are a = 1369, b = 1989, c = 2088 pm, β = 99.54°. The structure consists of tetraphenyl phosphonium cations and [OsCl3(NO)(SnCl3)2]2?-anions. In the anion the osmium is coordinated octahedrally by three chlorine atoms (mean bond length r Os? Cl 238 pm), two SnCl3 groups in transposition to each other (r Os? Sn 265 pm) and the N-atom of the covalently bonded nitrosyl ligand (r Os? N 173 pm). The i.r. spectrum of the anion is reported and assigned.  相似文献   

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Tetraphenylphosphonium tetraiodotrithiotriarsenate, PPh4[As3S3I4] PPh4[As3S3I4] is formed along with PPh4I3 and other unidentified compounds by the reaction of As2S3, PPh4I and HI in CH2I2 at 80°C. PPh4[As3S3I4] was characterized by its IR spectrum and an X-ray crystal structure determination (3684 unique observed reflexions, R = 0.083). Crystal data: a = 1390.3, b = 1548.9, c = 1505.4 pm, β = 91.08°, monoclinic, P21/c, Z = 4. The crystals are not isotypic with the corresponding chloro and bromo compounds, although the anion constitutions are of the same type. The [As3S3I4]? ion consists of an As3S3 ring in the chair conformation, the three As atoms are commonly linked to a bridging I atom and each As atom is bonded to one terminal I atom. Cations and anions are packed in alternating layers.  相似文献   

7.
PPh4[As3S3Cl4] and PPh4[As3S3Br4] When As2S3 reacts with PPh4X and HX in 1,2-C2H4X2 (X = Cl, Br), the title compounds are obtained as minor products; the main products are PPh4[As2SX5]. Their crystal structures were determined by X-ray diffraction. PPh4[As3S3Cl4]: a = 1187.7, b = 1090.9, c = 1191.8 pm, α = 82.91, β = 88,93, γ = 88.52°; twins with twin plane (100); R = 0.109 for 1618 observed reflexions of one twin crystal. PPh4[As3S3Br4]: a = 1119.7, b = 1177.5, c = 1204.1 pm, α = 81.59, β = 85.88, γ = 88.25°; R = 0.061 for 2331 observed reflexions. Both compounds crystallize in the space group P1 , Z = 2, and can be considered to be isotypic. Nevertheless, PPh4[As3S3Br4] does not form twins as PPh4[As3S3Cl4]. The crystals consist of PPh4+ and [As3S3X4]? ions. In the anions, the three As atoms of an As3S3 ring in the chair conformation are commonly joined to an X atom and each As atom is bonded to one further terminal X atom. Cations and anions are packed in alternating layers.  相似文献   

8.
Preparation, Mössbauer and Vibrational Spectra of the Complexes [SnCl4F]?, [SnCl4(NCS)]?, and [SnCl4(NCS)2]2? N(CH2)4F and N(CH2)4SCN react in liquid SO2 with SnCl4 yielding the adducts [N(CH3)4][SnCl4F] (I), [N(CH3)4][SnCl4(NCS)] (II) and [N(CH3)4]2[SnCl4(NCS)2] (III).respectively. Mössbauer and vibrational spectra indicate for the anion of I a fluoro-bridged species, which is probably tetrameric like the isoelectronic SbCl4F. For II dimeric moieties are proposed with bridging S-atoms, while [SnCl4(NCS)2]2? has an octahedral structure with N-bonded isothiocyanate groups in the trans-positions.  相似文献   

9.
Formation of PPh4[WOCl4 · THF] and PPh4Cl · 4As4S3 from W(CO)6 and PPh4[As2SCl5] and their Crystal Structures When W(CO)6 and PPh4[As2SCl5] are irradiated with UV light in tetrahydrofurane, PPh4[WOCl4 · THF], PPh4 Cl· 4As4S3 and PPh4[Cl2H] are obtained. X-ray crystal structure determinations were performed. PPh4[WOCl4 · THF], monoclinic, space group P21/c, Z = 4, a = 1207.5(2), b = 1003.7(2), c = 2642.0(5) pm, β = 114.71(1)°, R = 0.049% for 2824 reflexions; PPh4+ and [WOCl4. THF]? ions are present, the WOCl4 group having the shape of a tetragonal Pyramid with a short W ? O bond (169 pm) and the THF molecule being weakly associated (W? O 236 pm). PPh4Cl · 4AsS3, tetragonal, I41/a, Z = 4, a = 1742.3(3), c = 1664.5(4) pm, R = 0.066% for 1350 reflexions; it consists of separate PPh4+ and Cl? ions and As4S3 molecules.  相似文献   

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Reactions of Uranium Pentabromide. Crystal Structures of PPh4[UBr6], PPh4[UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN, and (PPh4)2[UO2Br4] · 2CH2Cl2 PPh4[UBr6] and PPh4[UBr6] · 2CCl4 were obtained from UBr5 · CH3CN and tetraphenylphosphonium bromide in dichloromethane, the latter being precipitated by CCl4. Their crystal structures were determined by X-ray diffraction. PPh4[UBr6]: 2101 observed reflexions, R = 0.090, space group C2/c, Z = 4, a = 2315.5, b = 695.0, c = 1805.2 pm, β = 96.38°. PPh4[UBr6] · 2CCl4: 2973 reflexions, R = 0.074, space group P21/c, Z = 4, a = 1111.5, b = 2114.2, c = 1718.7 pm, β = 95.42°. Hydrogen sulfide reduces uranium pentabromide to uranium tetrabromide. Upon evaporation, bromide is evolved from solutions of UBr5 with 1 or more then 3 mol equivalents of acetonitrile in dichlormethane yielding UBr4 · CH3CN and UBr4 · 3CH3CN, respectively. These react with PPh4Br in acetonitrile affording (PPh4)2[UBr6] · 4CH3CN, the crystal structure of which was determined: 2663 reflexions, R = 0.050, space group P21/c, Z = 2, a = 981.8, b = 2010.1, c = 1549.3 pm, β = 98.79°. By reduction of uranium pentabromide with tetraethylammonium hydrogen sulfide in dichloromethane (NEt4)2[U2Br10] was obtained; (PPh4)2[U2Br10] formed from UBr4 and PPh4Br in CH2Cl2. Both compounds are extremely sensitive towards moisture and oxygen. The crystal structure of the oxydation product of the latter compound, (PPh4)2[U02Br4]· 2 CH2Cl2, was determined: 2163 reflexions, R = 0.083, space group C2/c, Z = 4, a = 2006.3, b = 1320.6, c = 2042,5 pm, β = 98.78°. Mean values for the UBr bond lengths in the octahedral anions are 266.2 pm for UBr6-, 276.7 pm for UBr62? and 282.5 pm for UO2Br42?  相似文献   

12.
Summary The osmium(VII) salt (Ph4P)[OsO4] functions as a stoichiometric oxidant for benzylic and allylic alcohols, oxidising primary alcohols to aldehydes and secondary alcohols to ketones. Its vibrational spectra and cyclic voltammetric behaviour are compared with those of the perruthenate ion, [RuO4].  相似文献   

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The Crystal Packing in three Modifications of PPh4[ReO(S4)2] and PPh4[ReS(S4)2] Mixed crystals PPh4[ReS(S4)2]0,63[ReO(S4)2]0,37 were obtained from PPh4Cl, ReCl5 and Na2S4 in acetonitrile. Their crystal structure corresponds to the known structure of this kind of compound (space group P21/n). In a similar reaction with ReBr5 instead of ReCl5, PPh4[ReO(S4)2] was obtained in small yield. Its triclinic crystal structure was determined by X‐ray crystallography (space group P1). It contains cation pairs (PPh4+)2 such as they have been found in many other instances. In contrast, the crystal structures of the mixed crystals and of one known modification of PPh4[ReS(S4)2] have PPh4+ columns similar to compounds crystallizing in the space group P4/n, albeit in a severely distorted manner; their space group P21/n is a subgroup of P4/n with a doubled unit cell. In another modification of PPh4[ReS(S4)2] (space group P21/c) the columns are less distorted, but arranged in a different way.  相似文献   

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Synthesis, I.R. Spectrum, and Crystal Structure of PPh4[OsCl4(NO)(NSCl)] Molten trithiazyl chloride reacts with OsCl3(NO) to yield a product mixture consisting mainly of S4N3[OsCl4(NO)(NSCl)] and S4N3Cl. Extraction of this mixture with a solution of tetraphenylphosphonium chloride in dichloromethane affords green (PPh4)2[OsCl5(NO)] · 2 CH2Cl2 and the red title compound. PPh4[OsCl4(NO)(NSCl)] was characterized by its IR spectrum and an X-ray crystal structure analysis (3001 independent observed reflexions, R = 0.048). Crystal data: monoclinic, space group P21/c, Z = 4, a = 1716, b = 1054, c = 1588 pm, β = 96.25°. The compound consists of PPh4⊕ cations and [OsCl4(NO)(NSCl)]? anions in which the nitrosyl and the chlorothionitrene ligands have a cis arrangement. Due to positional disorder the NO and NSCl groups are superimposed statistically in the structure model.  相似文献   

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Thiochloroarsenates (III): Preparation, Vibrational Spectra, and Crystal Structures of PPh4[As2SCl5] and (PPh4)2[As2SCl6] · C2H4Cl2 PPh4[As2SCl5] can be obtained from As2S3 + PPh4Cl with HCl in CH2Cl2 or 1,2-C2H4Cl2. It reacts with a second mole of PPh4Cl to yield (PPh4)2[As2SCl6]. The latter also is formed by the reaction of As2S5 + 2 PPh4Cl with HCl, a second product being (PPh4)2[As2Cl8]. The i.r. and Raman spectra of the title compounds are reported. Their crystal structures were determined by X-ray diffraction. Crystal data: PPh4[As2SCl5], monoclinic, space group P21/n, a = 1175.8, b = 1508.0, c = 1593.4 pm, β = 96.22°, Z = 4; (PPh4)2[As2SCl6] · C2H4Cl2, triclinic, P1, a = 1166.3, b = 1188.2, c = 2044.6 pm, α = 95.47, β = 97.53, γ = 111.05°, Z = 2. Including the lone electron pairs, the coordination of the As atoms in the [As2SCl5] ion is distorted trigonal-bipyramidal with the S, one Cl atom, and an electron pair in equatorial positions; the two bipyramids around the two As atoms share a common edge. The As atoms in the [As2SCl6]2− ion have a distorted octahedral coordination, the two octahedra share a common face; the lone electron pairs are in the trans positions to the S atom.  相似文献   

19.
The binary zirconium and hafnium polyazides [PPh4]2[M(N3)6] (M=Zr, Hf) were obtained in near quantitative yields from the corresponding metal fluorides MF4 by fluoride–azide exchange reactions with Me3SiN3 in the presence of two equivalents of [PPh4][N3]. The novel polyazido compounds were characterized by their vibrational spectra and their X‐ray crystal structures. Both anion structures provide experimental evidence for near‐linear M‐N‐N coordination of metal azides. The species [M(N3)4], [M(N3)5]? and [M(N3)6]2? (M=Ti, Zr, Hf) were studied by quantum chemical calculations at the electronic structure density functional theory and MP2 levels.  相似文献   

20.
Tetraphenylphosphonium Heptathiacyclo Thioarsenate(III), PPh4[SAsS7] From PPh4[As2SCl5] und K2S5 the title compound was obtained in acetonitrile among other products. According to an X-ray crystal structure analysis, it crystallizes in the orthorhombic space group Pna21 with a = 1 826.1(3), b = 1 312.0(2), c = 1 215.9(2) pm, Z = 4. The structure consists of PPh4+ and [SAsS7]? ions, AsS7 rings in the crown conformation as in S8 being present.  相似文献   

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