New mixed tellurides of nickel and Group 13–14 metals Ni<Subscript>3−δ</Subscript>MTe<Subscript>2</Subscript> (M = Sn,In, Ga)

Three new mixed tellurides of nickel and group 13–14 metals Ni_3−δMTe₂ (M = Sn, In, Ga) were prepared by high-temperature ampoule synthesis and studied by powder X-ray diffraction analysis. The compound Ni_3−δSnTe₂ was also studied by single crystal X-ray diffraction analysis. The structural model of this phase and two analogs was described as consisting of layers with nickel-main group metal bonds confined from the above by tellurium atoms. The van der Waals gap formed through contacts between the tellurium atoms of neighboring layers is partially occupied by nickel atoms. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1879–1881, October, 2007.     

Thermoanalytische Untersuchungen an Schichtmaterialien: Der Einfluβ der Kationen auf das thermische Verhalten

Aluminium-free layered silicates of the metal silicate hydrate type (M-SH) comprise an interesting supplement to the well-known zeolite-like porous materials. Their specific properties allow these materials to be used as catalysts, adsorbents and ion-exchangers. Comparative X-ray diffraction and thermoanalytical investigations (TG and DSC) have shown that the thermoanalytical methods are useful to follow the process of structure formation of ilerite. The interlayer cations influence the properties of the different ilerites. In particular, the hydration behaviour of ilerite is affected. Thus, H⁺- and DTMA⁺-ilerite are stable up to temperatures of about 800°C, while the as-synthesized Na-form loses water irreversibly at about 150°C, is dehydroxylated, and is then desomposed structurally at about 400°C. The course of the dehydration exhibits significant differences for the various cation forms.This revised version was published online in November 2005 with corrections to the Cover Date.     

Novel gallium-mediated C3-allylation of indoles and pyrroles in aqueous media promoted by Bu4NBr

A mild and efficient protocol for the coupling of indoles and pyrroles with allyl halides such as allyl bromide, crotyl bromide and propargyl bromide in the presence of gallium metal in a Bu₄NBr-DMF-H₂O system has been developed. The reaction is equally effective when cadmium is used in lieu of gallium and the corresponding 3-allyl indoles and 3-allyl pyrroles were obtained in almost comparable yields.     

部分水解聚丙烯酰胺在多孔介质中的静态吸附研究——水解度对吸附量的影响

部分水解聚丙烯酰胺在多孔介质中的静态吸附研究———水解度对吸附量的影响杨继萍李惠生黄鹏程（北京理工大学化工与材料学院北京１０００８１）（北京航空航天大学材料科学与工程系北京１０００８３）关键词部分水解聚丙烯酰胺，水解度，多孔介质，静态吸附聚合物作为...     

Synthesis and Characterization of a New Layered Aluminophosphate [Al3P4O16][(CH3)2NHCH2CH2NH(CH3)2][H3O]

A new layered aluminophosphate, denoted AlPO-CJ12, has been synthesized in the system Al(OPrⁱ)₃-H₃PO₄-tetramethylethylenediamine-triethyleneglycol and its structure solved by single-crystal X-ray diffraction analysis. It is further characterized by X-ray powder diffraction, ICP, TG, DTA, and elemental analyses. The compound has an empirical formula of [Al₃P₄O₁₆][(CH₃)₂NHCH₂CH₂NH(CH₃)₂][H₃O], and crystallizes in the triclinic space group P-1 (No. 2) with a=8.9907(6) Å b=9.8359(6) Å, c=14.5566(8) Å, α=75.872(3)°, β=88.616(3)°, γ=63.404(3)°, Z=2, R₁=0.0451, and wR₂=0.1094. The alternation of tetrahedral AlO₄ and PO₃ (=O) units forms a sheet structure with a 4×6×8 network. The inorganic layers stacked in an AAAA sequence are held together by the protonated organic amine and water molecules. The co-templating role of the water molecules is studied by the calculation of the nonbonding host-guest interaction energies through a computational simulation.     

Effect of tetrahydrofuran on the conductance and ion-pairing of hydrogen chloride in wet and dry methanol mixtures

The molar conductance of dilute solutions of HCl in wet (68.5% methanol + 31.5% tetrahydrofurane mixtures at 25°C have been measured. The data were analyzed using the Fuoss-Hsia equation to calculate the infinite dilution molar conductances and association constants. The trend of the limiting conductances in these mixtures as a function of the water content shows, once more, the peculiar minimum due to the anomalous proton conductance mechanism. From these data the limiting molar conductance in the anhydrous binary solvent system was evaluated. The percentage excess proton mobility with respect to potassium ion has also been determined. All these data are compared to those found in a binary isodielectric methanol mixture containing as cosolvent 1,4-dioxane. This comparison shows that proton mobilities are very similar in both solvent mixtures. The dielectric constants, refractive indices, viscosities and densities of the methanol-tetrahydrofuran mixtures in the whole mole fraction range have been measured and are reported. An analysis of the excess molar volumes and viscosities shows a slight deviation of this system from ideality.     

混合价化合物的研究(Ⅱ)─—电化学及现场光谱电化学方法研究非质子介质中Dawson结构杂多阴离子[HAs_2Mo_(18)O_(62)]~(n-)的电还原性质

以电化学和现场紫外－可见－近红外及现场FTIR光谱电化学方法对Dawson结构杂多阴离子［HAS2Mo18O62］5－在非质子介质（CH3CN）中的电还原过程进行了研究．结果表明，该杂多阴离子在非质子介质中经历4步单电子还原反应，所产生的杂多蓝阴离子在近红外区出现宽广的价间电荷转移吸收带，而红外区Mo＝O端键及Mo—O—Mo桥键的特征吸收峰在还原后均有不同程度的红移．     

Conductance study of ammonium complexes with several crown ethers and cryptands in nitrobenzene,acetonitrile and dimethylformamide solutions

The formation of ammonium complexes with several crown ethers and cryptands in nitrobenzene, acetonitrile and dimethylformamide solutions was investigated by conductometry at 25°C. Stability constants of the resulting 1:1 complexes sere determined from the molar conductance-mole ratio data and found to vary in the order DC18C6>18C6>DB30C10>DB21C7>DB24C8>DB18C6>15C5>B15C5>12C4, in the case of crown complexes, and in the order C222>C221>C211>C22>C21 for the ammonium cryptates. The stabilities of the complexes varied inversely with the Gutmann donicity of the solvents. Influences of the number of members in the macrocycle, nature of the substituents in the polyether ring, cavity size and dimensionality, conformations of the free and complexed ligands and number of N⁺–H bonds available for hydrogen bonding are discussed.     

Novel reaction systems for the synthesis of O-glucosides by enzymatic reverse hydrolysis

Our studies are presented to replace alcohols as solvents in reverse hydrolytic reactions catalyzed by immobilized β-glucosidase to synthesize O-substituted β-d-glucopyranosides in preparative-scale. We found that 1,2-diacetoxyethane is a suitable solvent and O-alkyl or aryl β-d-glucosides were synthesized in moderate yields (after isolation 12-19%). In these reactions proportion of glucose and glucosyl acceptor hydroxy compounds was 1:20. We suggest that 1,2-diacetoxyethane can be useful not only for alcohols but for other glucosyl donor compounds unsuitable for the role of solvent (e.g., phenols) in the synthesis of O-β-d-glucosides by reverse hydrolysis.     

Solvothermal Synthesis and Crystal Structure of a Layered Thioantimonate(Ⅲ) [C4H9NH3]2Sb4S7

An inorganic-organic hybrid thioantimonate(Ⅲ) [CH3(CH2)3NH3]2Sb4S7 1 with layered structure was synthesized by solvothermal method.1 crystallizes in the triclinic system, space group P with a = 7.0124(11), b = 11.919(2), c = 14.879(3) (A), α = 108.791(3), β = 102.441(3), γ = 92.846(2)o, V = 1140.1(3) (A)3, Mr = 859.71, Z = 2, Dc = 2.504 g/cm3, μ= 5.324 mm-1, F(000) = 804, S = 1.013, the final R = 0.0297 and wR = 0.0618 for 3534 observed reflections with I＞2σ(I). 1 consists of [C4H9NH3] cations and two-dimensional [Sb4S7]n2n-anion which is composed of three SbS3 trigonal pyramids and one SbS4 unit joined by sharing common corners. The anionic layers are stacked perpendicularly to the c axis of the unit cell forming two-dimensional channels between the layers. The [C4H9NH3] cations interdigitate in a bilayer and reside in the 2D channels leading to a sandwich-like arrangement of the anion and cations.