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1.
A new method for silylation of allyl ethers with chlorosilanes has been developed by the use of Cp2TiCl2 as a catalyst. This reaction proceeds efficiently at −20 °C in THF using nBuMgCl. A plausible reaction pathway via allyltitanocene intermediate was proposed. 相似文献
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Contributions to the Chemistry of Halosilane Adducts. XXII. Hydrogen Bonding and Ionization of Pentacoordinated Si-Compounds. Preparation, Properties, Crystal and Molecular Structure of 2,2-Dimethyl-2,3-dihydro-1H-[1,4,2]diazasilolo[4,5-α]pyridinium-chloride-Chloroform(1/1), The title compound ( 1 ) is obtained by the reaction of 2-trimethylsilylaminopyridine and Me2CH2ClSiCl in CHCl3. The SiCl bond is ionic (X-ray structure determination). 1 crystallizes monoclinic space group P21/c (Z = 8). The asymmetric unit contains two symmetrically nonequivalent molecular cations of 1 , two Cl anions and two CHCl3. Silicon is tetracoordinate with Si? N-bond distances of 1.766 Å and 1.777 Å. The shortest SiCl distances (3.908 and 4.110 Å) correspond to ionic interactions. Both Cl anions are hydrogen bonded to CHC13. Additionally one C1? is hydrogen bonded to the NH groups of two neighbouring cations. Structural comparison with related compounds suggests these interactions to be responsible for the transition from pentacoordination to tetracoordination at Si (ionization of the Sic1 bond). 1H- and 29Si-NMR investigations of 1 show this transition to be dependent on the combined effect of NH…?C1? and C13CH…?C1? interactions. 1 is completely ionized in CDCl3 in the temperature range ?80° to +80°C while in the weaker acceptor solvent benzonitrile a temperature dependent shift from the ionic tetracoordinate to the pentacoordinate structure is observed with increasing pentacoordination with increase of temperature. 相似文献
3.
Eduardo Vyhmeister Anthony J. Muscat David Suleiman L. Antonio Estvez 《Fluid Phase Equilibria》2008,270(1-2):121-128
Fluid-phase equilibria, including dew points, bubble points, and critical points were measured for four binary systems composed of a chlorosilane and carbon dioxide. The measurements were carried out in a constant-composition, variable-volume cell equipped with a sapphire window, which allowed visual observation of the phases in the cell. A syringe pump was used to inject the CO2 into the cell and to control its pressure. Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, and diethyldichlorosilane up to about 0.14 mol fraction were studied in this apparatus and a total of 243 phase-boundary points were obtained. Displacements in the critical point with respect to pure CO2 of up to 11.81 MPa and 348.05 K were observed. Modeling of the fluid-phase equilibria for three of the four binary systems was done using the Peng–Robinson equation of state, standard van der Waals mixing rules with two binary interaction parameters, and a φ–φ formulation of the equilibrium. The binary interaction parameters were obtained by fitting the model to the experimental data. The model produced excellent agreement between computed and experimental data. Graphical representations of the modeling results are presented and compared to experimental results. The results indicate that the largest chlorosilane (diethyldichlorosilane) produced the largest shift in critical pressure and critical temperature with respect to pure CO2. 相似文献
4.
Paul F. Hudrlik Donghua Dai Anne M. Hudrlik 《Journal of organometallic chemistry》2006,691(6):1257-1264
Reactions of 1,4-dilithiobutadienes (from 1,4-diiodo-1,2,3,4-tetraethylbutadiene (1) and 2,2′-dibromobiphenyl (7) with t-BuLi) with Me3SiCl gave siloles (3 and 9a) as the major products. No evidence for a disilylated butadiene was obtained. Use of higher molecular weight chlorosilanes ((allyl)Me2SiCl, BnMe2SiCl, and PhMe2SiCl) with dibromide 7 gave dimethylsilole 9a and a silane (10a, 10b, or 10c) resulting from trapping of the organic group by the chlorosilane. 相似文献
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6.
Application of the Stabilized Koopmans’ Theorem to the Temporary Anion States of Chlorosilanes in Long‐Range Corrected Density Functional Theory
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The stabilized Koopmans’ theorem (SKT) is very successful in predicting relative vertical electron attachment energies in the Hartree‐Fock theory. It is mainly accomplished by systematically scaling the most diffuse functions in the basis set. Recently, the SKT has been extended to the temporary anion states (TASs) of polyatomic molecules in the long‐range corrected density functional theory. In this paper, this method will be further applied to chlorosilanes for their importance in the chemical processes of the semiconductor industry. Their resonance energies and lifetimes are determined by computing the density of resonance states via SKT. The detailed characteristics of resonance orbitals are then analyzed. It turns out that the lowest unfilled orbitals of chlorosilanes are essentially σ*Si‐Cl in character. Moreover, several TASs with strong Si/Cl “d” character have been identified. These results, definitely, will help us in understanding the peculiar bonding and chemical properties of chlorosilanes. 相似文献
7.
Makoto Tanabe 《Journal of organometallic chemistry》2011,696(6):1211-32
An incompletely condensed silsesquioxane containing trisilanol (c-C5H9)7Si7O9(OH)3 reacts with [PdI2(bpy)] (bpy = 2,2′-bipyridine) in the presence of Ag2O to produce a palladium complex with an O,O-chelating silsesquioxanate ligand, [Pd{O11Si7(c-C5H9)7(OH)}(bpy)] (1). The reaction of Ph2SiClH with 1 in 2:1 ratio causes disilylations of the silsesquioxanate ligand, forming [PdCl2(bpy)]. Addition of p-cresol to a solution of 1 yields the trisilanol and [Pd(OC6H4CH3-p)2(bpy)]. 相似文献
8.
本文从生产发展、生产技术、市场、技术开发等方面的动态,阐述有机硅材料工业现状,并预测今后发展方向和在信息社会中的地位与作用。 相似文献
9.
Norio Sakai Akimasa Watanabe Reiko Ikeda Yumi Nakaike Takeo Konakahara 《Tetrahedron》2010,66(46):8837-8845
The Me3SiCl-promoted intramolecular aminomethylation of a novel type of N,O-acetals, which were prepared via a facile three-step synthesis from N-alkylaniline derivatives and N-alkyl-2-oxazolidinones that leads to the production of pharmaceutically useful 1,4-benzodiazepine skeletons with a variety of functional groups is described. This method was successfully applied to the facile preparation of both tricyclic benzodiazepine derivatives and a 1,4-benzoxazepine derivative via 7-exo-trig cyclization. 相似文献
10.
五甲基环戊二烯是最重要的配位体,它通过电子效应和空间位阻能够稳定高价氧化态的金属,本文研究了五甲基环戊二烯锂与卤代硅烷反应,合成了6种五甲基环戊二烯基硅烷(2~7),其化学反应方程式如下: 相似文献