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861.
超声波作用下羰基化合物的还原偶联反应 总被引:5,自引:0,他引:5
超声波在一些有机反应中有明显的促进作用「“,Luche等认为超声波的作用有两种主要类型[’j.一类是涉及电子转移的自由基或离子一自由基型反应,由于超声波的空化作用所产生的局部高温高压可以促进电子转移,从而明显地加快反应速度;对大多数离子型反应,超声波只能起到机械的物理作用.我们曾报道偕二卤化合物在Li、Na、Mg等金属作用下产生卡宾的反应是单电子转移过程,该反应可由于超声辐射而大大加速[‘];而在芳基叔脚的断裂反应中,超声波可以促进三苯基俄与金属馊反应生成二苯基脚负离子,但对它进一步的亲核取代反应却没有明… 相似文献
862.
借助定量金相、扫描电子显微镜、透射电子显微镜等微观分析手段对钨质量分数为93%的钨合金在15~50GPa冲击压力下微观结构响应性态进行了考察,发现了一些钨合金所特有的现象,即钨颗粒与粘结相交界处出现成分迁移,新相析出;并结合断口分析,探讨了钨合金在冲击作用下发生断裂的微观特征与韧脆转化间的关系及其物理本质。 相似文献
863.
864.
A nickel catalyst was nodeled with ligand L^2,[NH=CH-CH=CH-0]^-,which should have potential use as a syndiotactic plyolefin catalyst,and the reaction mechanism was studied by theoretical calculations using the density functinal method at the B3LYP/LANL2MB level.The mechanism involves the formation of the intermediate [NiL^2Me]^ ,in which the metal occupies a T-shaped geometry.This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L^2.The results show that both structures can lead to the desired product via similar reaction paths,A and B.Thus,the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-0 or trans to the Ni-N bond in the catalyst.The polymerization process thus favors the catalysis of syndiotactic polyolefins.The syndiotactic synthesis effects could also be enhanced by varations in the ligand substituents.From energy considerations,we can conclude that it is more favorable for the methyl ttrans-O position to form a complex than to occupy the trans-N position.From bond length considerations,it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position. 相似文献
865.
The novel complex [K(18-C-6)]2[Cd(mnt)2][18-C-6-18-crown-6,nmt=1,2-dicyanoethene-1,2-dithiolate,C2S2-(CN)2^2-] was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complex displays two-dimensional network structure of [K(18-C-6)] complex segments and [Cd(nmt)2] complex segment bridged by S-K-S,S-K-N and N-K-N interactions between adjacent[K(18-C-6)] and [Cd(mnt)2]units. 相似文献
866.
贮氢材料电极循环寿命的定量预测定时放电半衰期法的应用韩剑文,袁满雪,周作祥,赖城明(南开大学化学系天津300071)关键词:贮氢电极,循环寿命,半衰期。前文 ̄[1]讨论了应用定终点电位放电半衰期法来预测贮氢材料电极循环寿命的问题。本文讨论如何采用定时... 相似文献
867.
Summary A sensitive precolumn fluorescence derivatization method for low level detection of the, volatile (N-nitrosodimethylamine and N-nitrosopyrrolidine) and non-volatile N-nitrosamines (N-nitrosoproline and N-nitrosodiethanolamine) an high-performance liquid chromatography was developed. This method is based on the denitrosation of the compounds of interest by a mixture of hydrobromic acid and acetic acid to produce the corresponding secondary amines. These are, then, able to react with, a quinolizinocoumarin derivative (luminarin 9®) to form highly fluorescent labelled N-nitrosamine derivatives. The structural elucidation of the luminarin 9® derivatives of N-nitrosoproline and N-nitrosodimethylamine by way of example, were established by liquid chromatography-mass spectrometry (LC-MS) and by direct chemical ionization-mass spectrometry (CI-MS). The separation, derivatization and detection conditioins were optimized for all the studied compounds. The detection limits (signal to noise ratio=3) were between 0.4 and 1.0 pmol injected depending on the compound. The calibration graphs were linear for derivatized amounts in the range of 0.5–40 nmol for N-nitrosodimethylamine and N-nitrosopyrrolidine, 0.4–2- nmol for N-nitrosoproline and 1.0–40 nmol for N-nitrosodiethanolamine. The repeatability (RSD less than 3.5%, n=6) and reproducibility (RSD less than 4.8%, n-6) were satisfactory. 相似文献
868.
Group theoretic methods are presented for the transformations of integrals and the evaluation of matrix elements encountered in multiconfigurational self-consistent field (MCSCF) and configuration interaction (CI) calculations. The method has the advantages of needing only to deal with a symmetry unique set of atomic orbitals (AO) integrals and transformation from unique atomic integrals to unique molecular integrals rather than with all of them. Hamiltonian matrix element is expressed by a linear combination of product terms of many-center unique integrals and geometric factors. The group symmetry localized orbitals as atomic and molecular orbitals are a key feature of this algorithm. The method provides an alternative to traditional method that requires a table of coupling coefficients for products of the irreducible representations of the molecular point group. Geometric factors effectively eliminate these coupling coefficients. The saving of time and space in integral computations and transformations is analyzed. © 1994 by John Wiley & Sons, Inc. 相似文献
869.
电化学法测定几种稀土贮氢合金的热力学函数 总被引:14,自引:0,他引:14
贮氢材料由于能可逆地吸放氢,得到了广泛地应用.特别是以贮氢材料为负极制成的氢镍二次电池,容量为同类型镉镍电池的1.5~2倍,且电压又相近,是镉镍电池的理想换代产品,受到人们普遍的关注。LaNi_(4.5)Mn_(0.5),LaNi_(4.9)Sn_(0.1)和La_(0.8)Nd_(0.2)Ni_(2.5)Co_(2.4)Al_(0.1)是电化学性能较优越的贮氢合金。LaNi_(4.5)Mn_(0.5)的电化学容量高,理论容量可达400mAh.g~(-1).LaNi_(4.9)Sn_(0.1)和La_(0.8) Nd_(0.2) 相似文献
870.
本文采用XE-60交联弹性石英性细管柱及407有机体埴充柱气色谱法可分分析丙烯腈中有机杂质。通过对柱长、担体粒度、液膜厚度、柱温和载气流量的选择。确定出最佳色 谱条件。 相似文献