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141.
ZrIV and TaV Complexes with Methano‐Bridged Bis(aryloxy) Ligands The bis(aryloxy) ligand precursor compounds bis(2‐trimethylsiloxy‐5‐tbutylphenyl)methane (L–SiMe3) and its bromoderivative (2‐trimethylsiloxy‐3‐bromo‐5‐tbutylphenyl)(2′‐trimethylsiloxy‐5′‐tbutylphenyl)methane (LBr–SiMe3) are prepared in analogy to the corresponding calixarenes in excellent yields. X‐ray structure analysis for LBr–SiMe3: space group P21/c, a = 12.462(7), b = 10.466(6), c = 23.315(14) Å, β = 105.02(4)°, V = 2937(3) Å3, Z = 4. L–SiMe3 and LBr–SiMe3 react with ZrIV and TaV chlorides in very good yields forming di‐ and trinuclear complexes. From the reaction of CpZrCl3 with LBr–SiMe3 in the ratio of 3 : 2 a Zr3 complex ( 7 ) is obtained, with one LBr ligand only, which Zr atoms are bridged by a μ3‐oxygen. The X‐ray structure analysis of 7 (space group R 3, a = 33.23(6), c = 24.47(8) Å, V = 23405(128) Å3, Z = 18) additionally reveals that one phenolato oxygen atom of the LBr ligand is terminally bound to a distorted tetragonal‐pyramidal coordinated Zr atom, while the second phenolato oxygen atom of the LBr ligand forms a bridge to another Zr atom with a distorted octahedral coordination. The third Zr atom is also found in a distorted octahedral coordination mode. The reactions of L–SiMe3 and LBr–SiMe3 with CpTaCl4 and TaCl5 yield dinuclear Ta complexes with a bridging bis(aryloxy) ligand. NMR spectroscopic data point out that the coordination of the bis(aryloxy) ligands in the Ta complexes very much resembles that in the Zr3‐complex with one terminal and one bridging phenolato oxygen atom. The Zr3 and the Ta complexes LBrTa2Cp2Cl6 and LTa2Cl8 were tested with respect to their catalytic properties in olefin polymerisation reactions in the presence of MAO. 相似文献
142.
143.
(S)-QUINAP reacted with [Ir(cod)Cl]2 to form a new chelating iridium complex in 77.4% yield. The iridium complex was proved to be a highly efficient catalyst for the enantioselective hydrogenation of olefins. 33.4-95.1% ee were obtained for the hydrogenation of unfunctionalized olefins and 90.8-96.1% ee were obtained for functionalized olefins. 相似文献
144.
Rieko Furuyama 《Journal of organometallic chemistry》2005,690(20):4398-4413
Based on new results as well as the reported data, the ethylene and propylene polymerization behavior of bis(phenoxy-imine) Ti complexes (Ti-FI Catalysts) combined with MAO (particularly that of their fluorinated versions) is discussed, with an emphasis on the characteristics and mechanisms of living ethylene and syndioselective living propylene polymerization. Unlike common living olefin polymerization catalysts, fluorinated Ti-FI Catalysts with MAO display thermally robust living behavior and polymerize ethylene in a highly controlled manner at temperatures as high as 50 °C. Additionally, despite being C2-symmetric catalysts, fluorinated Ti-FI Catalysts/MAO mediate highly syndioselective living propylene polymerization. Fluorinated Ti-FI Catalysts that we developed are the first examples of catalysts that induce the living polymerization of both ethylene and propylene. In addition, they are also the first examples of living and, at the same time, highly stereoselective propylene polymerization catalysts. The versatile and robust living nature of the fluorinated Ti-FI Catalysts allows the preparation of a wide variety of unique living polymers; some of which can even be produced catalytically. On the basis of theoretical calculations as well as experimental results, we conclude that these unusual polymerization features of fluorinated Ti-FI Catalysts originate from an attractive interaction between the ligand and a growing polymer chain and/or the fluxional character of the catalyst coupled with 2,1-regiochemistry. This is in stark contrast to group 4 metallocene catalysts, which control olefin polymerization mainly by repulsive interactions based on the rigidly organized ligand frameworks. 相似文献
145.
Microwave heating has been utilised for the cross-metathesis reaction of N-allyl amino acid substrates to generate olefin homodimers. Remarkable acceleration of the cross-metathesis reaction (minutes compared to hours) over conventional reflux heating was observed. In addition, improved reaction yields and similar E/Z ratios for the cross-metathesis products were achieved. 相似文献
146.
147.
本文以ClCCo_3(CO)_9,Et_4N[FeCo_3(CO)_(12)],Me_4N[Fe_6C(CO)_(16)]诸羰基簇为研究对象,采用激光等离子体源飞行时间质谱及量化计算相结合,对上述羰基簇合物结构及稳定性进行了研究,并将所得结果用于推论ClCCo_3(CO)_9及Et_4N[FeCo_3(CO)_(12)]的烯烃氢甲酰化反应活性中间体和α-Al_2O_3担载的相应簇合物的CO加氢活性物种。 相似文献
148.
Summary A new route for the preparation of a series of phenoxyacetaldehydes (2a–j) which are useful intermediates or products, is described. It starts from the easily available allylphenylethers1a–j which are ozonized at –40 °C and further treated with dimethylsulfide to give solutions of the corresponding phenoxyacetaldehydes2a–j; these are purified by column chromatography. Reaction of2a–j with 1-methyl-1-phenylhydrazine leads to the corresponding hydrazones3a–c,3e–g,3i, and3j. The aldehydes can also be transformed into the stable dimethylcetals4a,4e,4h, and4i by reaction with trimethyl orthoformate.
Ozonolyse von Olefinen, 8. Mitt. Synthese von Phenoxyacetaldehyden durch Ozonolyse von Allylphenylethern
Zusammenfassung Ein neuer Weg, die als Synthone nützlichen Phenoxyacetaldehyde2a–j darzustellen, wird beschrieben. Dazu werden die leicht zugänglichen Allylphenylether1a–j bei –40 °C ozonisiert und anschließend mit Dimethylsulfid reduziert, um Lösungen von2a–j zu erhalten. Reaktion von2a–j mit 1-Methyl-1-phenylhydrazin führt zu den entsprechenden N-Methyl-N-phenylhydrazonen3a–c,3e–g,ei und3j. Die Aldehyde können auch durch Reaktion mit Trimethylorthoformiat in die stabileren Dimethylacetale4a,4e,4h und4i übergeführt werden.相似文献
149.
150.
Amanda L. MacKinnon 《Journal of organometallic chemistry》2003,683(1):114-119
The compound trans-NiCl2(IPr)2 (IPr=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) is synthesized and characterized crystallographically. In combination with MAO, it is converted to an intermediate which catalyses the dimerization of ethylene but which not the polymerization of ethylene, propylene or 1-hexene. 相似文献