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21.
22.
The unseeded non-hydrolytic sol-gel synthesis of ZrW2O8 and ZrMo2O8 produces trigonal ZrM2O8 (M = W, Mo) at 740 and 300–400°C, respectively. Cubic ZrW2O8 can be prepared using non-hydrolytic sol-gel methods by seeding with small amounts of preprepared cubic material, and the formation of the trigonal polymorph can be suppressed completely. Seeds with a small particle size are necessary for the preparation of cubic ZrW2O8. In contrast, seeding of ZrMo2O8 gels with either cubic ZrMo2O8 or cubic ZrW2O8 only lowers the temperature at which the trigonal phase crystallizes. 相似文献
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24.
Reduction of ZrBr4 with HSnBu3 yielded a blue solid. When this blue solid was treated with PMe3, a hexanuelear cluster [Zr6Br14H4( PMe3)4] (2) was isolated. Reaction of the blue solid with [PPh4]Br in CH2Cl2 resulted in the formation of a paramagnetic and unstable cluster anion, [Zr6Br18H5]2– (3), which disproportionated to form a new cluster anion, [Zr6Br18H5]3– (4) and some Zr(IV) species. Compounds containing 4 can also be obtained from reaction of the blue solid with Br– in MeCN. Reduction of ZrCl4 with HsnBu3 gave a red–brown solid, and [Zr6Cl14H4(AsMe3)4] (9) and [Zr5Cl12H4(AsMe3)5](8) were obtained by reaction of the red–brown solid with AsMe3. No cluster compounds containing amine ligands were obtained in the reaction of the red–brown solid with amines; only compounds containing the [Zr6Cl18 H5]3– anion and ammonium cations were isolated. Altogether ten products were characterized by single crystal X-ray diffraction and where possible, by 1H NMR studies. 相似文献
25.
氯氧化镁在水中的溶解行为 总被引:3,自引:0,他引:3
用pH法和氯电位法测定氯氧化镁不同温度下在水中的溶解过程。一定间隔时间分析液样中的Mg^2+、Cl^-、OH^-的浓度,用物化方法鉴定固相。得出不同温度下的相转化、溶解的C ̄t曲线及动力学方程。计算了它们的Ksp和热力学函数。 相似文献
26.
Homoallylic ethers react with Cp2ZrCl2/2 n-BuLi reagent to afford cyclopropane derivatives. Cyclopropylcarbinyl-homoallyl rearrangements involving zirconium species are observed depending on the substrate structure. 相似文献
27.
B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究 Ⅰ.B2O3含量的影响 总被引:5,自引:2,他引:5
制备了不同B2O3含量(0~20%)的B2O3/TiO2-ZrO2固体酸催\r\n化剂,用XRD,FT-IR,N2吸附及NH3-TPD等方法测定了其结构、比表\r\n面积、孔分布和表面酸性.结果表明,当B2O3含量较低(≤5%)时,\r\n催化剂呈无定形态,样品中的B2O3主要以BO4结构存在.当B2O3含量较\r\n高(≥8%)时,催化剂中的TiO2-ZrO2以ZrTiO4晶相存在,分散于Ti\r\nO2-ZrO2表面的B2O3主要以玻璃体形式和BO3结构存在.随着B2O3含量\r\n的增加,催化剂的比表面积减小,孔径增大.300℃下的环己酮肟气相\r\nBeck-mann重排反应结果表明,随着B2O3含量的增加,己内酰胺的选择\r\n性逐渐增大,而己内酰胺的收率在B2O3含量为12%时达到最大值.讨论\r\n了B2O3/TiO2-ZrO2的催化性能与其表面酸性及孔径大小的关系. 相似文献
28.
Sizov A. I. Zvukova T. M. Belsky V. K. Bulychev B. M. 《Russian Chemical Bulletin》2001,50(11):2200-2202
The heterometallic zirconocene(iii) aluminum hydride complex (Cp2ZrH)2HAlCl2·C4H8O2·C6H6 was synthesized by reduction of Cp2ZrCl2 with lithium aluminum hydride in the presence of Cp2TiBH4 and 1,4-dioxane, and its structure was established by X-ray diffraction analysis. 相似文献
29.
Veiros LF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2505-2518
The mechanisms of three closely related reactions were studied in detail by means of DFT/B3 LYP calculations with a VDZP basis set. Those reactions correspond to 1) the reductive elimination of methane from [Zr(eta5-Ind)2(CH3)(H)] (Ind=C9H7-, indenyl), 2) the formation of the THF adduct, [Zr(eta5-Ind)(eta6-Ind)(thf)] and 3) the interconversion between the two indenyl ligands in the Zr sandwich complex, [Zr(eta5-Ind)(eta9-Ind)], which forms the link between the two former reactions. An analysis of the electronic structure of this species indicates a saturated 18-electron complex. A full understanding of the indenyl interchange process required the characterisation of several isomers of the Zr-bis(indenyl) species, corresponding to different spin states (S=0 and S=1), different coordination modes of the two indenyl ligands (eta5/eta9, eta5/eta5 and eta6/eta9), and three conformations for each isomer (syn, anti, and gauche). The fluxionality observed was found to occur in a mechanism involving bis(eta5-Ind) intermediates, and the calculated activation energy (11-14 kcal mol(-1)) compares very well with the experimental values. Two alternative mechanisms were explored for the reductive elimination of methane from the methyl/hydride complex. In the more favourable one, the initial complex, [Zr(eta5-Ind)2(CH3)(H)], yields [Zr(eta5-Ind)2] and methane in one crucial step, followed by a smooth transition of the Zr intermediate to the more stable eta5/eta9-species. The overall activation energy calculated (Ea=29 kcal mol(-1)) compares well with experimental values for related species. The formation of the THF adduct follows a one step mechanism from the appropriate conformer of the [Zr(eta5-Ind)(eta9-Ind)] complex, producing easily (Ea=6.5 kcal mol(-1)) the known product, [Zr(eta5-Ind)(eta6-Ind)(thf)], a species previously characterised by X-ray crystallography. This complex was found to be trapped in a potential well that prevents it from evolving to the 3.4 kcal mol(-1) more stable isomer, [Zr(eta5-Ind)2(thf)], with both indenyl ligands in a eta5-coordination mode and a spin-triplet state (S=1). 相似文献
30.
Esterification of carboxylic acids with alcohols is one of the most fundamental and useful transformations in organic synthesis. The most common catalysts are H2SO4 and TsOH. However, H2SO4 or TsOH-catalyzed esterification procedure has some problems such as corrosion, side reactions, difficulty in separation. Hence, recently, various solid acid catalysts such as ion-exchanged resins, molecular sieve, and heteropoly acids etc. have been employed for esterification reaction. However, the s… 相似文献