阳极氧化膜WO3（Ⅱ）：电显色的介质效应

用循环计时电量法、循环伏安法、电化学现场(in-situ)紫外可见反射光谱技术和光电流谱技术研究了溶剂和阳离子(H~+,Li~+)对阳极氧化膜WO_3电显色稳定性和过程的影响。从循环计时电量图可以测定表征膜稳定性的氢或锂的累积量和暂态周期数。实验发现W/WO_3/LiCLO_4乙腈溶液体系具有高的电显色稳定性。引起WO_3膜可逆电显色的H~+和Li~+离子的嵌-脱过程的界面电化学机理不同。着色态WO_3膜的色心是自由电子,其密度超过10~(21)/cm~3,生色机理是等离子体振荡。     

Remarkable reactivity enhancement with Sb?N inter-coordination of ethynyl-1,5-azastibocines in Pd-catalyzed cross-coupling reactions with organic halides

The reaction of 12-arylethynyl-6-methyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]-azastibocines with organic halides such as acyl halides and aryl halides in the presence of PdCl₂(PPh₃)₂ as a catalyst led to the formation of cross-coupling products, alkynyl ketones and diaryl acetylenes, in good yields. The reactivity of the ethynyl group on the 1,5-azastibocines was far superior to that on diphenyl(phenylethynyl)stibane, which brought about marked improvement in the reaction conditions (lower temperature and shorter reaction time) and in the yields of the cross-coupling products. Single-crystal X-ray analysis of the ethynyl-1,5-azastibocine showed the presence of intramolecular Sb?N interaction which should be responsible for the remarkable reactivity enhancement of the 1,5-azastibocines for this type of reaction.     

d,h-m̈-Alkoxoalkylphosphonato-e-m̈-alkoxo-f-m̈-oxo-bis[trichloroantimon(V)]-Verbindungen

d,h-m?-Alkoxoalkylphosphonato-e-m?-alkoxo-f-m?-oxo-bis[trichloroantimony(V)] Compounds The binuclear antimony(V) complexes Cl₃Sb(O)[R³(R¹O)PO₂](OR²)SbCl₃ 1 to 7 with R¹, R² and R³ = Me or Et in solution slowly exchanges the R² groups between the equatorial oxygen atoms of the Sb₂O₂ ring. The SbO(3)PO(3)Sb ringsystem makes rapid pseudorotation. The resulting isomeres are detected by nmr spectroscopy.     

Einfache Trithio- und Perthiocarbonatokomplexe mit interessanter Koordinationschemie: [E(CS3)2]2− (E = Sn,Zn, Cd), [E(CS3)3]3− (E = As,Sb, Bi,Co), {Cu(CS3)−}∞ und [Zn(CS4)2]2−

Simple Trithio- and Perthiocarbonato Complexes with Interesting Bond Properties: [E(CS₃)₂]^2? (E = Sn, Zn, Cd), [E(CS₃)₃]^3? (E = As, Sb, Bi, Co), {Cu(CS₃)^?}_∞ and [Zn(CS₄)₂]^2? By reactions of potassium trithiocarbonate ( 1 ) with solutions of zinc(II)- acetylacetonate, cadmium(II)-chloride, tin(II)-chloride, arsenic(III)-sulfide (suspension), antimony(III)-chloride, bismuth(III)-chloride and copper(II)-chloride in dimethyl sulfoxide, as well as of trisodium hexanitrito cobaltate(III) in water, and the precipitation of the complexes with an aqueous solution of tetraphenylphosphonium chloride the compounds (PPh₄)₂[Zn(CS₃)₂] ( 2 ), (PPh₄)₂[Cd(CS₃)₂] ( 3 ), (PPh₄)₂[Sn(CS₃)₂] ( 4 ), (PPh₄)₃[As(CS₃)₃] ( 5 ), (PPh₄)₃[Sb(CS₃)₃] ( 6 ), (PPh₄)₃[Bi(CS₃)₃] ( 7 ), (PPh₄)₃[Co(CS₃)₃] ( 8 ) and (PPh₄)Cu(CS₃) ( 9 ) have been isolated. (PPh₄)₂[Zn(CS₄)₂] · CH₃NO₂ ( 10 ) has been prepared by heating a solution of 2 in nitromethane to 60--70°C in presence of air. The reaction of 1 in dimethyl sulfoxide with an aqueous tetraphenylphosphonium chloride solution in presence of oxygen leads to (PPh₄)₂[C₂S₆] ( 11 ). The compounds have been characterized by spectroscopical studies (IR, Raman, UV/Vis, ¹¹³Cd/⁵⁹Co-NMR), magnetic susceptibility measurements, powder diffractometry, elemental analyses and single crystal X-ray structure analysis ( 4 – 7 , 10 and 11 ). The difficult growing of single crystals has been reported in detail. For crystal data see Inhaltsübersicht.     

XRD法研究CrO3与NaY、NaM分子筛的表面相互作用

负载于多孔性、高比表面载体上的三氧化铝是重要的工业催化剂，多年来人们对催化剂中Croa的存在状态以及与载体的相互作用进行了广泛的研究［‘－4］，发现CrO。能在载体表gn散成非晶相的表面化合物，非晶相Cr（VI）具有较高的催化活性．我们曾经对MoO。／NaY，MoO。／NaM体系进行过系统的研究，发现MOO。与分子筛载体间存在强表面相互作用［’］．在此研究基础上，选择了CrO3／NaY、CrO。／NaM体系，采用XRD法对上述体系进行了研究．结果表明170oC下晶相CrO。能在NaY、NaM分子筛上自发分散成非晶相Cr（VI），且分散量大．C…     

Chemistry of polyfunctional molecules-123. Reactions of BiBr3, SbI3 and AsI3 with LiN(PPh2)2; X-ray structure of a cyclophosphazene salt containing arsenic(I)

BiBr₃ or SbI₃ react at 20°C with LiN(PPh₂)₂ (1) to give elementary Bi or Sb and the P---P coupled phosphazene ligand Ph₂P---N=PPh₂---PPh₂=N---PPh₂ (2). The reaction of AsI₃ with 1 at room temperature formed yellow needles of the eight-membered heterocycle (3), whereas AsI₃ interacted at 80°C with 1 in the molar ratio of 1:3 to give elementary arsenic and 2. Treatment of AsI₃ and 1 at 20°C in a 1:2 stoichiometry yielded the seven-membered, cyclic arsenium(I) salt

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I·4THF (5·4THF), which was characterized by elemental analysis, conductivity, mass, IR and NMR spectroscopy and single-crystal X-ray structural analysis.     

一个新颖的三维异核锑(III)-镨(III)配合物[Sb2-μ4-(EDTA)2Pr(H2O)5]NO3•4H2O的合成、晶体结构及热分解研究

合成了锑-镨与乙二胺四乙酸形成的新颖三维配合物[Sb₂-μ₄-(EDTA)₂Pr(H₂O)₅]NO₃•4H₂O, 用元素分析、红外光谱、热分析及X射线单晶衍射法等进行了组成和结构表征. 结果表明该配合物属正交晶系, 空间群Pnn2; 晶胞参数: a＝1.07031(2) nm, b＝2.30805(4) nm, c＝0.72343(2) nm, V＝1.78711(7) nm³, Z＝2, D_c＝2.202 g/cm³, F(000)＝1164, μ＝2.955 mm^－1, GOF＝1.000, 最终偏离因子R₁＝0.0203, wR₂＝0.0545 [I＞2σ(I)]. 在标题化合物中, 每个镨(III)离子的配位数为9, 与五个水分子中的五个氧原子和四个羧基氧原子配位, 形成三帽三角棱柱空间配位多面体. 锑(III)与EDTA离子中的四个氧原子和两个氮原子配位, 在赤道平面上有一孤对电子. 同时讨论了配合物的热分解过程.     

First structural characterization of binary AsIII and SbIII azides

The highly explosive molecules As(N(3))(3) and Sb(N(3))(3) were obtained in pure form by the reactions of the corresponding fluorides with (CH(3))(3)SiN(3) in SO(2) and purification by sublimation. The crystal structures and (14)N NMR, infrared, and Raman spectra were determined, and the results compared to ab initio second-order perturbation theory calculations. Whereas Sb(N(3))(3) possesses a propeller-shaped, pyramidal structure with perfect C(3) symmetry, the As(N(3))(3) molecule is significantly distorted from C(3) symmetry due to crystal packing effects.     

Electrochromic and structural characteristics of mesoporous WO<Subscript>3</Subscript> films prepared by a sol-gel method

The preparation of electrochromic films of mesoporous tungsten trioxide from tungstic acid and tungstic hexaethoxide precursors with the addition of an organic stabiliser via a sol-gel method is reported. These films have been structurally characterised and both the film morphology and crystalline composition of the films were found to be significantly dependent on the temperature at which the films were annealed and upon the choice of precursor. Films annealed at lower temperatures consisted of amorphous and hexagonal tungsten trioxide, whereas films annealed above 500 °C comprised solely of monoclinic WO₃. The electrochromic activity of the films was found to be equally dependent on method of preparation, and both the composition and the structure of the WO₃ films were shown to clearly influence the colouration efficiency of the films.Dedicated to Zbigniew Galus on the occasion of his 70^th birthday.     

Total synthesis of 3,3′:4′,3″-ter-1,2,5-thiadiazole using a synthetic utility of S4N4·SbCl5 complex

3,3′:4′,3″-Ter-1,2,5-thiadiazole, an useful oligoheterocyclic compound, has been accomplished in seven steps from 1-(5-methyl-3-isoxazolyl)ethanone or diethyl acetylenedicarboxylate using a synthetic utility of tetrasulfur tetranitride antimony pentachloride (S₄N₄·SbCl₅) complex to make a 1,2,5-thiadiazole ring.