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排序方式: 共有103条查询结果,搜索用时 15 毫秒
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Arndt P Baumann W Spannenberg A Rosenthal U Burlakov VV Shur VB 《Angewandte Chemie (International ed. in English)》2003,42(12):1414-1418
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V. V. Burlakov A. V. Letov P. Arndt W. Baumann A. Spannenberg Ch. Fischer L. I. Strunkina M. Kh. Minacheva Ya. S. Vygodskii U. Rosenthal V. B. Shur 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):63-67
Zwitterionic titanoxanes {Cp[η5-C5H4B(C6F5)3]Ti}2O (I) and {(η5-iPrC5H4)[η5-1,3-iPrC5H3B(C6F5)3]Ti}2O (II), which contain two positively charged Ti(IV) centres in the molecule, are able to catalyse the ring-opening polymerization of -caprolactone (-CL) in toluene solution and in bulk. The process proceeds with a noticeable rate even at room temperature and accelerates strongly on raising the temperature to 60 °C. The best results have been obtained on carrying out the reaction in bulk. Under these conditions, the use of I as a catalyst (-CL:I = 1000:1) gives at 60 °C close to quantitative yield of poly--CL with the molecular mass of 197 000. An increase in the -CL:I ratio to 6000:1 increases the molecular mass of poly--CL to 530 000. Tetrahydrofuran (THF) is also polymerized under the action of I albeit with a lesser rate. However, the molecular mass of the resulting poly-THF can reach rather big values under optimal conditions (up to 217 000 at 20 °C and the THF:I ratio of 770:1). A rise in the reaction temperature from 20 to 60 °C results here to a decrease in the efficiency of the process. Titanoxane II is close to I in its catalytic activity in the -CL polymerization but it is much less active in the polymerization of THF. Propylene oxide (PO), in contrast to -CL and THF, gives with I only liquid oligomers in wide temperature and PO:I molar ratio ranges (−30 to +20 °C, PO:I = 500–2000:1). γ-Butyrolactone and 1-methyl-2-pyrrolidone are not polymerized under the action of I at room temperature. The reactions found are the first examples of catalysis of the cationic ring-opening polymerization by zwitterionic metallocenes of the group IVB metals. 相似文献
4.
Paul‐Michael Pellny Vladimir V. Burlakov Wolfgang Baumann Anke Spannenberg Uwe Rosenthal 《无机化学与普通化学杂志》1999,625(6):910-918
The reactions of the bis(trimethylsilyl)acetylene permethylmetallocene complexes CpM(η2‐Me3SiC2SiMe3) (M = Ti ( 1 ), M = Zr ( 2 )) with H2O and CO2 were studied and compared to those of the corresponding metallocene complexes Cp2M(L)(η2‐Me3SiC2SiMe3) (M = Ti ( 3 ), L = – ; M = Zr, L = THF ( 4 )) to understand the influence of the ligands Cp(η5‐C5H5) and Cp*(η5‐C5Me5) as well as the metals titanium and zirconium on the reaction pathways and the obtained products. In the reaction of the permethyltitanocene complex 1 with water the dihydroxy complex CpTi(OH)2 ( 5 ) was formed. This product differs from the well‐known titanoxane Cp2TiOTiCp2 which was obtained by the reaction of the corresponding titanocene complex 3 with water. The reaction of the permethylzirconocene complex 2 with water gives the mononuclear alkenyl zirconocene hydroxide 6 . An analogous product was assumed as the first step in the reaction of the corresponding zirconocene complex 4 with water which ends up in a dinuclear zirconoxane. In the conversion of the permethylzirconocene complex 2 with carbon dioxide the mononuclear insertion product 7 was formed by coupling of carbon dioxide and the acetylene. In contrast, the corresponding zirconocene complex 4 affords, by an analogous reaction, a dinuclear complex. In additional experiments the known complex CpZr(η2‐PhC2SiMe3) ( 8 ) was prepared, starting from CpZrCl2 and Mg in the presence of PhC≡CSiMe3. This complex reacts with carbon dioxide resulting in a mixture of the regioisomeric zirconafuranones 9 a and 9 b . From these in the complex 9 a , having the SiMe3 group in β‐position to the metal, the Zr–C bond was quickly hydrolyzed by water to give the complex CpZr(OH)OC(=O)–C(SiMe3)=CHPh ( 10 a ) compared to complex ( 9 b ) which gives slowly the complex CpZr(OH)OC(=O)–CPh=CH(SiMe3) ( 10 b ). 相似文献
5.
A random network model containing defects has been developed and applied to the deposition of amorphous SiOx films on a flat substrate. A new Monte Carlo procedure enables dangling bonds to migrate and annihilate. The degree of porosity in the films is found to increase with oxygen content. As the oxygen content increases a larger fraction of pore surfaces is covered with oxygen, and the density of dangling bonds on pore surfaces decreases. Oxygen plays the role of a surfactant, lowering the energies of pore surfaces and enhancing the porosity of amorphous SiO2 compared to amorphous Si. 相似文献
6.
We use tools of the equilibrium statistical mechanics of disordered systems to study analytically the statistical properties of an ecosystem composed of N species interacting via random mutual interactions, as well as via deterministic self-interactions of order p>/=2. We show that the main effect of increasing the order of the interactions among the species is to make the system less competitive, in the sense that the fraction of extinct species is greatly reduced. In addition, we find that for p>2 there is a threshold value which gives a lower bound to the concentration of the surviving species, preventing then the existence of rare species and, consequently, increasing the robustness of the ecosystem to external perturbations. 相似文献
7.
Gimenez-Lopez Mdel C Räisänen MT Chamberlain TW Weber U Lebedeva M Rance GA Briggs GA Pettifor D Burlakov V Buck M Khlobystov AN 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):10977-10985
Anisotropy of intermolecular and molecule-substrate interactions holds the key to controlling the arrangement of fullerenes into 2D self-assembled monolayers (SAMs). The chemical reactivity of fullerenes allows functionalization of the carbon cages with sulfur-containing groups, thiols and thioethers, which facilitates the reliable adsorption of these molecules on gold substrates. A series of structurally related molecules, eight of which are new fullerene compounds, allows systematic investigation of the structural and functional parameters defining the geometry of fullerene SAMs. Scanning tunnelling microscopy (STM) measurements reveal that the chemical nature of the anchoring group appears to be crucial for the long-range order in fullerenes: the assembly of thiol-functionalized fullerenes is governed by strong molecule-surface interactions, which prohibit formation of ordered molecular arrays, while thioether-functionalized fullerenes, which have a weaker interaction with the surface than the thiols, form a variety of ordered 2D molecular arrays owing to noncovalent intermolecular interactions. A linear row of fullerene molecules is a recurring structural feature of the ordered SAMs, but the relative alignment and the spacing between the fullerene rows is strongly dependent on the size and shape of the spacer group linking the fullerene cage and the anchoring group. Careful control of the chemical functionality on the carbon cages enables positioning of fullerenes into at least four different packing arrangements, none of which have been observed before. Our new strategy for the controlled arrangement of fullerenes on surfaces at the molecular level will advance the development of practical applications for these nanomaterials. 相似文献
8.
Normen Peulecke Andreas Ohff Wolfgang Baumann Rhett Kempe Vladimir V. Burlakov Uwe Rosenthal 《Journal of organometallic chemistry》1996,520(1-2):235-239
The reaction of Cp2Zr(L)(η2-Me3SiC2) (L = THF, py) with equimolar amounts of H2C = CMe-CHO at room temperature depends strongly on the ligands L and the solvents that are used. With L = THF, in the THF solution the insertion product 1 was isolated, whereas by conducting the reaction in n-hexane solution an alkyne substitution with 1,4-coordination of the methacrolein takes place and the binuclear complex [ 2 was obtained. In conttrast, with L = py (a stronger ligand) only a 1:1 ratio of 1 and 2 was observed in both THF and in n-hexane. At 50°C complex 1 was converted into 2 and the alkyne was eliminated quantitatively.
Complexes 1 and 2 were characterized by IR and NMR spectroscopical measurements and 1 by an additional X-ray structure determination. 相似文献
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Burlakov VV Arndt P Baumann W Spannenberg A Rosenthal U Parameswaran P Jemmis ED 《Chemical communications (Cambridge, England)》2004,(18):2074-2075
The 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene (bis-titanocene-mu-(Z)-1,2,3-butatriene complex)3 is formed starting from [Cp2Ti(eta2-Me3SiC2SiMe3)] by in situ generated titanocene and 1,4-dichlorobut-2-yne via the 1-titanacyclobut-3-yne (2). 相似文献