三苯基锡(Ⅳ)N-烃基哌嗪氨荒酸酯配合物的合成、表征、性质和Ph3SnS2CN(C2H4)2NCH3的晶体结构

Six triphenyltin(Ⅳ)N-alkylpiperazinyldithiocarbamates have been synthesized by the reaction of triphenyltin chloride with N-alkylpiperazinyldithiocarbamates and characterized by elemental analysis, UV, IR and ¹H NMR. The crystal structure of Ph₃SnS₂CN(C₂H₄)₂NCH₃(1) has been determined by X-ray single crystal diffraction. The crystal of the compound 1 belongs to triclinic with space group P1, a=1.033 56(18) nm, b=1.148 8(2) nm, c=1.191 6(2) nm, α=66.282(2)°, β=78.756(2)°, γ=67.476(2)°， Z=2, V=1.195 2(4) nm³, D_c=1.460 g·cm^-3, μ=1.256 mm^-1, R=0.025 1, wR=0.058 3. The structure shows a distorted tigonal bipyramidal configuration with five-coordination for the central tin atom. CCDC: 240375.     

铋配合物[Bi(S2CNC5H10)2(NO3)]·[1，10-Phen]·0.5H2O的合成及晶体结构

The bismuth complex with dithiopiperdylcarbamate [Bi(S₂CNC₅H₁₀)₂(NO₃)]·[1，10-Phen]·0.5H₂O was synthesized. The crystal and molecular structure were determined by X-ray single crystal diffraction. The crystal belongs to monoiclinic with space group C2/c, a=3.140(2) nm, b=1.176 4(9) nm, c=2.021 6(15) nm, β=103.081(12)°, V=5.713(7) nm³, Z=8, F(000)=3064, D_c=1.815 g·cm^-3, μ=6.502mm^-1. The final R₁=0.0332, wR₂=0.040 3. In the complex, the bismuth atom is eight-coordinated in a capped distorted pentagonal bipyramidal geometry. CCDC: 222655.     

混配配合物[Zn(CF3COO)2(C7H6NS)2]的合成、晶体结构及表征

A mixed complex [Zn(CF₃COO)₂(C₇H₆NS)₂] was synthesized based on the reaction of Zn(CF₃COO)₂ and 2-aminobenzothiazol (C₇H₆NS) in methanol. The structure of the complex was characterized by elemental analysis, IR, ¹H NMR and thermal analysis. The crystal structure of the complex was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group C2/c, a=3.174 3(9) nm, b=1.010 0(3) nm, c=1.723 1(5) nm, β=118.841(4)°, V=4.839(2) nm³; D_c=1.625 g·cm^-3; Z=8; F(000)=2 368; μ=1.266 mm^-1. CCDC: 600233.     

铋(Ⅲ)四氢吡咯氨荒酸配合物[Bi(S2CNC4H8)3]2的合成和晶体结构

The novel bismuth(Ⅲ) complex with dithiotetrahydropyrrolocarbamate, [Bi(S₂CNC₄H₈)₃]₂ has been synthe-sized. The crystal structure has been determined by X-ray single crystal diffraction. The crystal belongs to mono-clinic with space group C2/c, a=1.6356(9) nm, b=1.1875(6) nm, c=2.3954(13) nm, β=100.741(8)°, Z=4, V=4.571(4) nm³, D_x=1.882g·cm^-3,μ=8.267mm^-1, F(000)=2512, R=0.0404, wR=0.0622. In this binuclear complex, each Bi(Ⅲ) is seven coordinate with a distorted pentagonal bipyramidal geometry. CCDC: 179924.     

具有N…Cu作用的一维链状配合物Cu(C8H9N2O2)2的合成和晶体结构

The title complex Cu(L)₂ (HL=o-vanillin hydrazone) was synthesized by the reaction of Cu(CH₃COO)₂·H₂O with o-vanillin hydrazone in the ethanol. It was characterized by elemental analysis, IR and X-ray single crystal structure analysis. The crystal of the title complex [Cu(C₈H₉N₂O₂)₂] belongs to triclinic, space group P1 with a=0.457 57(8) nm, b=1.333 2(2) nm, c=1.386 0(3) nm, α=108.955(2)°, β=90.868(2)°, γ=95.859(2)°, V=0.794 4(2) nm³, Z=2, D_c=1.647 Mg·m^-3, μ=1.406 mm^-1, F(000)=406, and final R₁=0.035 1, wR₂=0.096 3. The complex comprises a four-coordinated copper(Ⅱ) center, with an N₂O₂ planar coordination environment. The molecules are packed in one-dimensional chain polymer though the N…Cu interaction from adjacent molecules, respectively. CCDC: 634854.     

三元混合配合物Cu(C10H8N2O3)·(C5H5N)·(H2O)的合成和晶体结构

The novel copper(Ⅱ) complex with 2-oxo-propionic acid benzoyl hydrazone and pyridine ligands, Cu(C₁₀H₈N₂O₃)·(C₅H₅N)·(H₂O) (C₁₀H₈N₂O₃^2- is the dinegative ion of 2-oxo-propionicacid benzoyl hydrazone), has been synthesized and characterized by elemental analysis and IR. The crystal structure of the title complex was determined by single crystal X-ray diffraction technique. Complex crystallized in the triclinic space group P1 with a = 0.729 08(10) nm, b= 1.020 01(14) nm, c= 1.126 28(15) nm, α = 71.644(2) °, β = 80.437(2) °, γ = 89.160(2)°, V= 0.78328(18) nm³, Z= 2, D_c= 1.547 Mg·m^-3, μ(MoKα) = 1.417 mm^-1, F(000) = 374. The final R₁ = 0.030 6, wR₂= 0.084 2 for 2 992 observed reflections [I≥2σ(I)] out of 3357 unique reflections. In this complex, copper(Ⅱ) ion is square-pyramidally coordinated by two oxygen atoms and one nitrogen atom of tridentate C₁₀H₈N₂O₃^2- ligand, one nitrogen atom of the pyridine ligand, and one oxygen atom of water molecule with the oxygen atom of water molecule locating at the apical position. The analysis of the crystal structure indicates that the complex has a one-dimensional chain structure, which is formed by intermolecular hydrogen bonds. CCDC: 222656.     

二聚体有机锡配合物{[n-Bu2Sn(O2CCH2CS2NC4H8)]2O}2的合成，表征及晶体结构(英)

The title compound, {[n-Bu₂Sn(O₂CCH₂CS₂NC₄H₈)]₂O}₂, has been synthesized by the reaction of (tetrahydro-pyrrodithiolocarbamoylthio)acetic acid with the di-n-bubyltin oxide in 1∶1 molar ratio. The complex has been characterized by elemental analysis, IR and NMR. The crystal structure of it has been determined by X-ray single crystal diffraction. And the results showed that the crystal belongs to triclinic system with space group P1 and some crystal parameters: a=1.220 2(9) nm, b=1.315 8(10) nm, c=1.380 4(10) nm, α=111.215(9)°， β=99.357(9)°， γ=96.075(10)°, V=2.006(2) nm³, Z=1, F(000)=908, μ=1.489 mm^-1, D_c=1.474 g·cm^-3, R₁=0.037 5, wR₂=0.0839. The complex has a centrosymmetric dimer structure mode with a four-membered central endo-cyclic Sn₂O₂ unit in which two bridged oxygen atoms both connect with an exo-cyclic tin atom which has a distorted octahedron. Each of the endo-cyclic tin atoms exhibits a distorted trigonal bipyramid coordination geometry with an additional weak coordination carboxylate oxygen. Four carboxylate ligands are divided into two types. And two of them are bidentate and connecting to each of exo-cyclic tin atoms by using both oxygen atoms, whereas the others bridge to each pair of exo-and endo-cyclic tin atoms utilizing one oxygen atom only. CCDC: 220513.     

梯形结构有机锡配合物{[(p-MeC6H4CH2)2Sn]2(O)(Cl)OC2H5}2的合成和晶体结构

The title compound {[(p-MeC₆H₄CH₂)₂Sn]₂(O)(Cl)OC₂H₅}₂ was synthesized by the reaction of bis(p-met-hylbenzyl)tin dichloride with KOH in ethanol. The crystal structure of the complex has been determined by X- ray diffraction. The crystal belongs to monoclinic, space group P2₁/c with a=1.114 0(19) nm, b=2.423 1(3) nm, c=2.521 1(3) nm, β=99.398(3)°, V=6.714(16) nm³, Z=4, D_c=1.493 g·cm^-3, μ(Mo Kα)=15.94 cm^-1, F(000)=3 024, R₁=0.049 9, wR=0.101 7. The crystal structure shows that the coordination geometry of tin is a distorted trigonal bipyramid, and the ladder-like structure is shaped by three Sn₂O₂ planar four-membered rings. CCDC: 639682.     

二(o-氟苄基)锡双(四氢吡咯二硫代氨基甲酸酯)和二(p-氯苄基)锡双(二甲基二硫代氨基甲酸酯)的合成、表征及晶体结构

Di(o-fluorbenzyl)tin bis(dithiotetrahydropyrrolcarbamate) (1) and di(p-chlorbenzyl)tin bis(dithiomethylcarbamate) (2) were synthesized. Their structure were characterized by elementary analysis, IR and ¹H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of complex 1 belongs to orthorhombic with space group Pccn, a=2.096 1(12) nm, b=1.018 5(6) nm, c=1.205 9(7) nm, Z=4, V=2.574(2) nm³, D_c=1.624 g·cm^-3, μ(MoKα)=1.348 mm^-1, F(000)=1 272，R₁=0.038 7, wR₂=0.088 5. The crystal of complex 2 belongs to monoclinic with space group C2/c, a=1.531 3(16), b=1.868 4(19), c=0.951 8(10) nm, β=112.602(14)°, Z=4, V=2.514(5) nm³, D_c=1.612 g·cm^-3, μ(MoKα)=1.572 mm^-1, R₁=0.025 4, wR₂=0.070 4. In the complexes 1 and 2, the structures consist of discrete molecules containing six-coordinate tin atom in a distorted octahedron configuration. In crystal of complex 1, molecules are packed in the unit cell in one-dimensional chain structure through a S…S interaction between adjacent molecule. CCDC: 225420, 1; 225421, 2.     

Vapour-liquid equilibrium data for the systems C2H6 + N2, C2H4 + N2, C3H8 + N2, and C3H6 + N2

High pressure vapour-liquid equilibrium data for the C₂H₆ + N₂, C₂H₄ + N₂, C₃H₈ + N₂, and C₃H₆ + N₂ systems are presented. The data are obtained isothermally in the range from 200 K to 290 K. For each point of data, temperature, pressure and liquid and vapour phase mole fractions are measured.Values for the vapour phase mole fractions are calculated from the obtained pressure, temperature and liquid phase mole fractions. The calculated values are compared with the experimental results, and it is found that the average mean deviation between calculated and experimental mole fractions is less than 0.009 for the systems considered in this work.     

Synthesis and structures of triphenylbismuth diaroxides Ph3Bi(OAr)2, Ar = C6H3(Br2-2,4), C6H2(Br2-2,6)(NO2-4), and C6H2[(NO2)3-2,4,6]

Triphenylbismuth diaroxides Ph₃Bi(OAr)₂ (Ar = C₆H₃(Br₂-2,4) (I), C₆H₂(Br₂-2,6)(NO₂-4) (II), and C₆H₂[(NO₂)₃-2,4,6] (III) are synthesized in yields up to 74% by the reaction of triphenylbismuth with phenols in the presence of hydrogen peroxide (taken at a molar ratio 1: 2: 1, respectively) in ether. According to X-ray diffraction data, the bismuth atoms in compounds I-III have distorted trigonal-bipyramidal coordination with the aroxyl substituents in the axial positions; the Bi-C, Bi-O bond lengths and the OBiO, CBiC angles vary in the intervals 2.162–2.204, 2.150–2.299 ? and 172.4°–176.1°, 109.6°–139.9°, respectively. Compound II exhibits intramolecular contacts between the central atom and ortho-Br atoms (3.924, 4.101 ?), and compound III has similar contacts of the Bi atom with the O atoms of the ortho-nitro groups (3.114, 3.313 ?). Original Russian Text ? V.V. Sharutin, I.V. Egorova, O.K. Sharutina, A.P. Pakusina, M.A. Pushilin, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 1, pp. 14–21.     

Reactions of C2(a 3πu) with CH4, C2H2, C2H4, C2H6, and O2 using multiphoton UV excimer laser photolysis

C₂(a ³π_u) disappearance rate constants of 1.44, 0.96, 0.0296, 0.0130 and < 10^?6(x10^?10cm³s^?1) are reported for reactions with C₂H₄, C₂H₂, O₂, C₂H₆, and CH₄, respectively at 298 K. C₂(a ³π_u) fragments are generated by multiphoton ArF excimer laser photodissociation at C₂H₂, and monitored by dye laser induced fluorescence. Arguments are presented which favor chemical reactions over the C₂(a ³π_u) → (X ¹σ⁺_g) quenching channel. C₂ + C₂H₂ represents the one possible exception to the reactive channel.     

Vibrational spectra and internal rotation barriers of cyclopentadienyl germanium trihalides: (C5H5)GeCl3, (C5H5)GeBr3 and (C5H5)GeI3

IR and Raman spectra of gaseous and solid CpGeX₃ species (Cp  C₅H₅ and X = Cl, Br, I) are reported. The results are compared with those obtained previously for CpTiCl₃. Internal rotation barriers and thermodynamic functions are reported.     

Synthesis and crystal structures of (C8h8)Nd(C5H9C5H4) (THF)2 and [(C8H8)Gd(C5H9C4H4(THF)][(C8H8)GD(C5H9C5H4(THF)2]

LnCl₃ (Ln=Nd, Gd) reacts with C₅H₉C₅H₄Na (or K₂C₈H₈) in THF (C₅H₉C₅H₄ = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C₅H₉C₅H₄)LnCl₂(THF)_n (orC₈H₈)LnCl₂(THF)_n], which further reacts with K₂C₈H₈ (or C₅H₉C₅H₄Na) in THF to form the litle complexes. If Ln=Nd the complex (C₈H₈)Nd(C₅H₉C₅H₄)(THF)₂ (a) was obtained: when Ln=Gd the 1 : 1 complex [(C₈H₈)Gd(C_%H₉)(THF)][(C₈H₈)Gd(C₅H₉H₄)(THF)₂] (b) was obtained in crystalline form.

The crystal structure analysis shows that in (C₈H₈)Ln(C₅H₉C₅H₄)(THF)₂ (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η⁵), cyclooctatetraenyl (η⁸) and two oxygen atoms from THF are coordinated to Nd³⁺ (or Gd³⁺) with coordination number 10.

The centroid of the cyclopentadienyl ring (Cp′) in C₅H₉C₅H₄ group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd³⁺ (or Gd³⁺). In (C₈H₈)Gd(C₅H₉C₅H₄)(THF), the cyclopentyl-cyclopentadienyl (η⁵), cyclooctatetraenyl (η⁸) and one oxygen atom are coordinated to Gd³⁺ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd³⁺, which is almost in the plane (dev. -0.0144 Å).     

Die Trennung von Ar und O2 sowie CH4, C2H6, C3H8 und C4H10

Ohne Zusammenfassung     

Synthesis and crystal structure of Ir(C2H4)2(C5H7O2)

We report a new synthesis and characterization of Ir(C₂H₄)₂(C₅H₇O₂) [(acetylacetonato)-bis(η²-ethene)iridium(I)], prepared from (NH₄)₃IrCl₆ · H₂O in a yield of about 45%. The compound has been characterized by X-ray diffraction crystallography, infrared, Raman, and NMR spectroscopies and calculations at the level of density functional theory. Ir(C₂H₄)₂(C₅H₇O₂) is isostructural with Rh(C₂H₄)₂(C₅H₇O₂), but there is a substantial difference in the ethylene binding energies, with Ir-ethylene having a stronger interaction than Rh-ethylene; two ethylenes are bound to Ir with a binding energy of 94 kcal/mol and to Rh with a binding energy of 70 kcal/mol.     

Lutetium complexes with the 1,3-diphenylcyclopentadienyl ligand. Syntheses and molecular structures of the complexes {(Ph2C5H3)Lu(C2Ph4)(THF)} and {(Ph2C5H3)LuCl2(THF)3}

The reaction of LuCl₃(THF)₃ with Na(1,3-Ph₂C₅H₃) followed by the in situ reaction with Na₂[Ph₄C₂] produced (1,3-Ph₂C₅H₃)Lu(Ph₄C₂)(THF) (1). The structure of 1 was established by X-ray diffraction. In the crystal structure of 1, the bis-allyl η⁶-coordination of the tetraphenylethylene dianion to the lutetium cation was observed. The structures of (1,3-Ph₂C₅H₃)LuCl₂(THF)₃ and (C₅H₅)LuCl₂(THF)₃ were determined by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1912–1918, October, 2007.     

Evidence for the distortion of C2H4 and C2H2 chemisorbed on W(100)

The adsorption of C₂H₄ on W(100) has been studied by ultraviolet photoelectron spectroscopy with hν = 21.22 eV. The spectrum measured after in initial saturation exposure at 80 K exhibits structure which correlates well with energy levels recently calculated by Demuth and Eastman (DE) for sp³ rehybridized C₂H₄. Dehydrogenation of the adsorbate, either by subsequent heating to 295 K or direct adsorption at 295 K, yields a spectrum which correlates with DE's calculation for sp² rehybridized C₂H₂. These results suggest that C₂H₄ and C₂H₂ may be distorted from their planar and linear structures respectively and that the CC bonds on these molecules are stretched by adsorption on W(100). Qualitative arguments suggest that the bonding site for both melecules is directly over a W atom and that the Dewar—Chatt model for πd bonding in organometallic compounds is applicable.