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891.
《Journal of organometallic chemistry》2007,692(25):5633-5645
Triorganotin(IV) chlorides containing one LCN chelating ligand were hydrolyzed with an excess of sodium hydroxide. The composition of the products is strongly dependent on the nature of the organic groups bound to the tin atom. Di(n-butyl)tin, dimethyltin as well as the diphenyl derivative exhibits an equilibrium between hydroxide and stannoxane forms (oxide), whereas alkyltin species react spontaneously and reversibly with carbon dioxide present in the air to form carbonate species. On the other hand, diphenyl derivatives display virtually no reaction with CO2 towards carbonates, while the di-t-butyl-substituted tin derivative is stable under the same experimental condition and remains as a tin hydroxide. In the case of the dimethyltin derivative, a methyl group migration was observed with displacement of one LCN chelating ligand during the reaction on the air. The coordination geometry of the tin central atom(s) of all studied compounds can be described as trigonal bipyramidal with a dative bonded dimethylamino group occupying one coordination site. The catalytic activity of these compounds in transesterification reactions is generally lower compared to the systems reported in the literature, with the exception of the transesterification of ethyl acetate by cyclohexanol which displays a remarkable activity. 相似文献
892.
Dehui Sun Hongjie Zhang Jilin Zhang Jiangbo Yu 《Journal of solid state chemistry》2007,180(1):393-399
A novel supramolecular compound 1,6-hexanediamine trimolybdate ((C6H18N2)[Mo3O10], denoted as HDAMo) has been synthesized by a hydrothermal method and its structure has been characterized by elemental analyses, Fourier transform infrared (FT-IR) spectra, single-crystal X-ray diffraction (XRD) technique. This single crystal compound consists of protonated 1,6-hexanediamine (HDA) cations and polyoxometalate [Mo3O10]2− anions. Its crystal structure belongs to monoclinic system (space group P21/n) with a=7.7508(14), b=11.467(2), c=16.167(3) Å, β=92.689(3)°, V=1435.3(5) Å3, Z=4 and Dcalc=2.619 g cm−3. The final statistics based on F2 are GOF=0.980, R1=0.0261 and wR2=0.0506 for I>2σ(I). XRD analysis revealed that in the crystal structure of HDAMo, novel infinite [Mo3O10]2− chains parallel to a axis are made up of distorted MoO6 octahedra connected by corners and edges. The protonated HDA cations occupy channels formed by [Mo3O10]2− chains and exhibit strong hydrogen bond interactions to terminal and bridging oxo groups of the chains. The [Mo3O10]2− chains linked through protonated HAD cations formed a one-dimensional network. The HDAMo compound shows novel photochromic properties, i.e., its color changes from white to reddish brown gradually under UV irradiation. XRD, FT-IR, ESR spectra and XPS are used to investigate the photochromic behavior of the compound. 相似文献
893.
Summary Crystals of (NH3OH)3GaF6 have been isolated from aqueous solution. The compound crystallizes triclinic, with cell parametersa=6.539(5) Å,b=6.924(5) Å,c=9.403(1) Å, =87.01(9)°, =83.98(8)°, =70.28(8)°. The thermal decomposition was studied by TG and DSC analysis. 相似文献
894.
Stable monolayers of electropolymerized poly-N-vinylcarbazole (EPVK) and arachidic acid(AA) are obtained on a subphase of alkaline Tl2O3 colloidal solutions. As revealed by the atomic force microscope, there is phase separation in the mixed LB monolayers. Transmission electron microscopic observations reveal that ordered arrays of composite Tl2O3/Epvk nanowires are formed in the mixed monolayers. Formation of the composite nanowire arrays is attributed to the ordered adsorption of Tl2O3 colloidal particles along the polycationic EPVK chains. The composite nanowire array is 3.2nm wide with a spacing of 2.7nm.The composite nanowire arrays can also be formed when pure EPVK is used. Composite LB multilayers of Tl2O3/EPVK nanowire arrays are prepared. The bilayer spacing is 5.54nm.The present study is of importance to the fabrication of inorganic semiconductor/functional polymer composite nanowires. 相似文献
895.
V. Maleev M. SemenovV. Kashpur T. BolbukhA. Shestopalova D. Anishchenko 《Journal of Molecular Structure》2002,605(1):51-61
The aim of this paper is to summarize the original results concerned with the elucidation of the role of water environment in the formation of different structures of polyribocytidylic acid (poly(rC)), depending on the pH, temperature and ion content. To solve this problem, we studied the hydration of poly(rC)-K+ in films differing in water content, by methods of infrared spectroscopy and piezogravimetry, and in solution, using the dielectric measurements at a wavelength of 7.6 mm (extremely high frequencies — EHF). The experimental results were confirmed by a Monte Carlo simulation of the interaction between water molecules and single-strand and double-strand poly(rC) fragments in clusters of 800 water molecules. A model of hydration of double-strand complex of poly(rC)+-poly(rC) has been proposed based on our results and the known X-ray parameters of the complex. The obtained results and proposed structure of poly(rC)+-poly(rC) suggest that, the stabilization of this complex occurs due to intra- and inter-chain water bridges, together with the hydrogen bonds between neutral and protonated cytosines in pairs. 相似文献
896.
E. K. Starostin A. V. Ignatenko M. A. Lapitskaya K. K. Pivnitsky G. I. Nikishin 《Russian Chemical Bulletin》2001,50(5):833-837
A convenient method for the synthesis of - and ( – 1)-acetylenic acids involves free-radical oxidative scission of cycloalkanones containing five-, six, or seven-membered cycles to give the corresponding -olefinic acids followed by bromination of the latter and subsequent dehydrobromination under the action of alkalis. 相似文献
897.
V. M. Timoshenko Ya. V. Nikolin A. N. Chernega E. B. Rusanov Yu. G. Shermolovich 《Chemistry of Heterocyclic Compounds》2001,37(4):470-476
The reaction of 1,1-dihydropolyfluoroalkyl benzyl sulfones with sodium azide or trimethylsilyl azide in the presence of tertiary amines gives ammonium salts of 4-benzylsulfonyl-5-polyfluoroalkyl--triazoles. The proposed reaction scheme includes the participation of catalytic amounts of azide ion in the cyclization of the formed intermediate vinyl azides to triazoles. X-ray analysis of 1,4-diazabicyclo[2.2.2]octane salt of 4-benzylsulfonyl-5-(-H-hexafluoropropyl)--triazole has been carried out. 相似文献
898.
K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2. 相似文献
899.
V. P. Kazakov A. I. Voloshin S. S. Ostakhov N. Sh. Ableeva 《Russian Chemical Bulletin》1995,44(3):432-436
The thermal decomposition of dispiro(1,2-dioxetane-diadamantane) (1) sorbed on silipore containing EuCl3 ando-phenanthroline was investigated. The observed chemiluminescence is caused by radiative deactivation of EU*(iii) formed according to an energy transfer mechanism. Chemiluminescence decay in the course of the decomposition of1 is exponential with the rate constantk. The activation parameters of the decomposition of1 sorbed on silipore were determined from the temperature dependence ofk. These parameters are independent of the Eu(iii) content. A kinetic compensating effect was found: the dependence of logA onE
a as a function of the content of1. The mechanism of the compensating effect is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 447–451, March, 1995. 相似文献
900.
The effects of the composition of MnII, CoII or NiII nitrate hydrate — acrylamide (AAM) mixtures and of the duration of their aging at ambient temperature on the structurization of acrylamide complexes and on the character of their thermal polymerization have been studied by scanning and isothermic differential calorimetry. Structurization is a rather prolonged step in the synthesis of acrylamide complexes. The peculiarities and rate of this step are determined by the composition of the mixture and by the nature of the complexforming compound; it yields several structural modifications of the AAM complexes. The thermal polymerization of those structural forms of acrylamide complexes that polymerize at low temperatures may be formally described as polymerization in an acrylamide-nitrate-water mixture. The effective activation energy of the polymerization of acrylamide mixed with MnII nitrate hydrate is 45 kJ mol–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 679–683, April, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research, Project No. 93-03-4162. 相似文献