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61.
Matthias Weil 《Journal of solid state chemistry》2003,172(1):35-44
Mercury(I) selenite(IV) is polymorphic and crystallizes at least in three modifications, named α-, β-and γ-Hg2SeO3. Polycrystalline β-Hg2SeO3 was prepared by precipitation of a concentrated mercurous nitrate solution with selenous acid. Hydrothermal treatment of the colorless β-Hg2SeO3 powder in demineralized water at 250°C (10 days) yields light-yellow single crystals of α-Hg2SeO3 which show the highest density of the three modifications. Colorless needle-shaped single crystals of β-Hg2SeO3 and very few single crystals of γ-Hg2SeO3 co-crystallize from strongly diluted Hg2(NO3)2 and H2SeO3 solutions and were grown by a diffusion technique. All crystal structures were solved and refined from single crystal diffractometer data sets and are based on Hg22+ dumbbells and trigonal pyramidal SeO32− anions as the main building units. A common structural feature of all modifications is the formation of open channels extending parallel to the shortest crystallographic axis. The non-bonding orbitals of the SeIV atoms are stereochemically active and protrude into the channels. Upon heating in an open system under N2 atmosphere, both α- and β-Hg2SeO3 decompose in a well-separated three-step mechanism. The first step (T > 250°C) involves disproportionation into elementary mercury and α-HgSeO3 which at ca. 400°C subsequently transforms into β-HgSeO3. The second step between T = 400 and 500°C is accompanied by a loss of Hg and SeO2 and the formation of the basic salt Hg3SeO6. In the third step, at temperatures between T = 500° and 600°C, this material decomposes completely. Upon heating in a closed system (sealed silica capillaries), β-Hg2SeO3 transforms between 320-340°C into the more dense α-Hg2SeO3 which on further heating likewise converts into elementary mercury and β-HgSeO3. 相似文献
62.
Egon Fanghnel Hagen Bartossek Ute Baumeister Matthias Biedermann Helmut Hartung 《Journal of heterocyclic chemistry》1998,35(6):1449-1454
The first synthesis of substituted 2,2-dioxo-1-phenyl-1H-thieno[3,4-c][1,2]thiazines 2 and some of their reactions are achieved. Compounds 2 were prepared from the 3,5-dimethyl-1,1-dioxo-1,2-thiazine-4-carbaldehydes 1 by reaction with sulfur and triethyl amine in dimethylformamide under mild conditions. They were characterized spectroscopically and by X-ray structure analysis. The formylation, chlorination and oxidation of 2 are reported. 相似文献
63.
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65.
Martina Dotzler Astrid Schmidt Jochen Ellermann Falk A. Knoch Matthias Moll Walter Bauer 《Polyhedron》1996,15(24):4425-4433
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 I·4THF (5·4THF), which was characterized by elemental analysis, conductivity, mass, IR and NMR spectroscopy and single-crystal X-ray structural analysis. 相似文献
66.
67.
Matthias Deppner 《Journal of organometallic chemistry》2005,690(12):2861-2871
The synthesis is described of symmetric alkylidene bridged dinuclear zirconocene complexes. The influence of structural parameters and different cocatalysts such as methylaluminoxane (MAO), triphenyl tetrakis(pentafluorophenyl)borate- or tris(pentafluorophenyl)borane has been investigated for homogeneous propylene polymerization. The dinuclear catalysts show highest polymerization activities by activation with MAO. Activation with triphenyl tetrakis(pentafluorophenyl)borate results in polypropylenes with the highest degree of isotacticity. Compared to the mononuclear reference catalyst the dinuclear MAO activated complex achieved higher propylene polymerization activity and the polypropylene obtained from the dinuclear complex has a higher molecular weight than that one that was produced with the mononuclear complex. 相似文献
68.
The mechanism of reductive etherification reactions between aromatic aldehydes and alcohols has been investigated with the DFT(B3LYP)/6-31G method. One or two BH(3) molecules have been used to simulate the role of the catalyst and reducing agent. The solvent effects of the title reactions have been studied by the PCM model. It is found that the reactions between aromatic aldehydes and primary, secondary, and tertiary alcohols can proceed more easily in a polar solvent such as acetonitrile. The results provide evidence in theory to broaden the applications of reductive etherification reactions for the optimization of the radiochemical synthesis process of (18)F-labeled ether radiotracers. 相似文献
69.
The source of the effect of N-alkylation on the redox properties of Ni(II/I) and Cr(III/II) cyclam complexes has been investigated using DFT calculations. The structures of the anhydrous and hydrated complexes were optimized in the gas phase, and single point calculations were performed in a polarized continuum. The main results are the following: the decrease in outer sphere solvation upon N-alkylation is the major source of the relative stabilization of the lower oxidation state complexes by the tertiary amine ligands; tertiary amine nitrogen donors are stronger sigma-donors than the secondary amines, as predicted from the inductive effect of alkyls; steric strain elongates the metal-nitrogen bonds in the tertiary complexes and decreases the ligand strain energies; and the site of water binding to the complexes differs because of their different electronic structures (i.e., in the Ni complexes, the water molecules bind to the M[bond]N[bond]H sites, whereas in the Cr complexes they bind to the central metal cation). Outer sphere hydrogen bonding of water to the ligands in the coordination sphere lowers the ionization potentials by charge delocalization. 相似文献
70.
Annals of Global Analysis and Geometry - In the present paper, we consider star-shaped mean convex hypersurfaces of the real, complex and quaternionic hyperbolic space evolving by a class of... 相似文献