1-[(Z)-2-(-苯基二溴化锡基)乙烯基]环戊醇的合成及晶体结构

通过１［（Ｚ）２（三苯基锡基）乙烯基］环戊醇与Ｂｒ２反应制得了新化合物１［（Ｚ）２（苯基二溴化锡基）乙烯基］环戊醇．通过元素分析、锡含量测定、ＩＲ、１ＨＮＭＲ对其进行了表征并用Ｘ射线衍射法测得了所合成化合物的晶体结构．该化合物属正交晶系，Ｐ２１２１２１空间群，晶胞参数：ａ＝０８６７５（４）ｎｍ，ｂ＝１２５２３（７）ｎｍ，ｃ＝１４００９（８）ｎｍ；Ｚ＝４，Ｖ＝１５２１９ｎｍ３，Ｄｃ＝２．３９ｃｍ３，ｕ＝２３．７２ｃｍ－１．结构分析表明，标题化合物分子为畸变的三角双锥构架，双键的两个氢取顺式结构，分子中Ｏ与Ｓｎ配位，形成五元螯合环结构     

(Z)-1-[2-(苯基溴氯化锡基)乙烯基]-1-环己醇的晶体结构和反应机理

有机锡化合物的抗癌活性与结构的关系是人们所关注的一个重要课题[1.2].自1989年以来,我们合成了几个系列的C-Sn直接相连并在分子中存在O→Sn内配位的有机锡化合物[3]．经过抗癌活性实验,发现其中有很多种具有较高的抗癌活性．本文所报道的标题化合物分子有两种构型,迄今为止未见类似的报道．标题化合物的抗癌活性正在测试中．1实验部分1．且仪器1106型元素分析仪;锡含量用重量法分析;NicoletR。M／E四圆衍射仪．1．2标题化合物的合成（Z）－l｛2－（二苯基演化锡基）乙烯基11一环己醇（I）按照文献［"方法合成．产率80％,m．卜14…     

巯基葡聚糖凝胶分离富集催化动力学光度法测定痕量锡(Ⅳ)

研究在稀硫酸介质中,以锡(Ⅳ)催化溴酸钾氧化铍试剂Ⅰ的褪色反应及其动力学条件,测定锡(Ⅳ)的范围为0～40μg/L:检测限为1.63×10-8g/L.采用巯基葡聚糖凝胶(SDG)分离富集,使方法的选择性得到了大大的提高,可用于多种样品中痕量锡(Ⅳ)的测定,结果令人满意.     

新试剂2-(2-苯并噻唑偶氮)-5-氨基苯甲酸与铂(Ⅳ)的显色反应研究

合成了新试剂2-(2-苯并噻唑偶氮)-5-氨基苯甲酸(BTABA),研究了新试剂与铂(Ⅳ)的显色反应,先后在pH 4左右的乙酸盐缓冲及H2SO4和H3PO4混合介质中,在表面活性剂CTMAB存在下,形成了配位比为Pt(Ⅳ)∶BTABA=1∶2的红褐色配合物,其最大吸收波长为612 nm,表观摩尔吸光系数为1.12×105L.mol-1.cm-1。铂含量在0~30.0μg/25 mL范围内服从比耳定律。应用于Pt-C催化剂中铂的测定,结果满意。     

三(对氰基苄基)氯化锡的合成及晶体结构研究

苄基锡化合物因其具有丰富的反应性、结构特征及抗癌活性而引起人们的兴趣,最近我们合成了一系列的卤代苄基锡化合物,并报导了它们的晶体结构。在研究中我们发现苯环上连有的取     

二安替比林-(2-甲氧基)-苯基甲烷光度法测定铬

合成了新试剂二安替比林－（2－甲氧基）－苯基甲烷（DAoMM）；研究了在Mn（Ⅱ）存在下，DAoMM与Cr（Ⅵ）生成橙黄色化合物。该化合物最大吸收位于480nm；表观摩尔吸收系数为ε=1．58×105L·mol－1·cm－1和ε2=9．85×104L·mol－1·cm－1化合物至少稳定20h。服从比尔定律范围0～1．6×102μg／LCr（Ⅵ）和2×102～8×102μg／LCr（Ⅵ）。用于含铬废水和电镀废液中铬的测定，结果满意。     

(Z)-1[2-(苯基二溴化锡基)乙烯基]-1-环己醇的合成及晶体结构

报道了标题化合物〔C14H18Br2OSn〕的合成及晶体结构。该晶体属于单斜晶系，空间点群为P21/c，晶胞参数a=11.711(2)，b=9．114（2），c=16．864（3）A，β=102.94（1）°，V=1604.55（0）A3，Mr=480．78，Z=4，Dc=1．99g／cm3，u=65．20cm－1，F（000）=919，R=0．050，Rw=0．050．晶体结构由直接法解出。标题化合物分子中的锡原子被配体的2个碳、2个溴和1个氧原子配位，配位原子呈畸变的三角双锥构型，环已基为椅式构象，五员杂环为信封构象。     

一种合成2-(对硝基苯氧基)乙醇的新方法

报道了一种简便合成2－（4－硝基苯氧基）乙醇的新方法，其结构由熔点，IR和1H NMR确定。该化合物是一个结构较为简单的有机小分子，但它的合成却不是很容易。     

胍基稀土配合物[(CH2)5NC(NiPr)2]3Yb的合成及晶体结构

胍基可以通过改变氮上的取代基来调控配合物的空间及电荷效应，它们作为辅助配体用于稀土金属配合物的合成得到了人们的广泛关注。本文通过胍基锂盐和无水YbCl3以3：1的摩尔比进行复分解反应，合成了均配型稀土化合物[(CH2)5NC(N^iPr)2]3Yb，测得它为正交品系，     

有机锡配合物[(o-Cl-PhCH2)2Sn(OCOC9H6N)2]·2(C6H6)的合成和晶体结构研究

0引言某些有机锡羧酸酯化合物具有杀虫、杀菌和抗癌活性,引起人们极大的兴趣[1~3]。近年来的研究结果表明,该类化合物中心锡原子的配位形式既决定于与锡原子直接相连的烃基的结构,也与配体的类型有关,尤其是含有孤电子对的杂环酸的引入,导致了许多新型结构有机锡化合物的产生[4     

H_2O_2氧化N_2生成N_2O和H_2O机理的研究

采用量子化学计算方法研究了Ｈ２Ｏ２ 氧化Ｎ２ 生成Ｎ２Ｏ 和Ｈ２Ｏ 的机理．结果发现, Ｈ２Ｏ２ 氧化Ｎ２ 先通过１ 个四元环过渡态形成中间体Ｈ２Ｎ２Ｏ２ 分子,Ｈ２Ｎ２Ｏ２ 再通过一个五元环过渡态形成Ｎ２Ｏ和Ｈ２Ｏ．根据计算得到的每步反应的活化能,得知Ｈ２Ｏ２ 氧化Ｎ２ 生成中间体Ｈ２Ｎ２Ｏ２ 分子是整个反应的控制步骤．     

吸附法脱除乙烯中少量氮气的研究

采用重量法在电子天平上，研究了C2H4和N2单组分在5A、13X、丝光沸石和炭分子筛不同吸附剂上的吸附平衡性质和扩散动力学性质。单柱模拟变压吸附评价了炭分子筛吸附脱除C2H4-N2（N2为4．7％）混合组分中N2的性能，并对流速和压力的影响进行了考察。研究表明，该炭分子筛是吸附脱除C2H4中少量N2的理想吸附剂。     

Energetic and topological analysis of the reaction of Mo and Mo2 with NH3, C2H2, and C2H4 molecules

The Density functional theory has been applied to characterize the structural features of Mo(1,2)-NH(3),-C(2)H(4), and -C(2)H(2) compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo(1,2)-NH(3)), the interaction between Mo (or Mo(2)) and C(2)H(4) (or C(2)H(2)) are the low-spin (Mo-C(2)H(4) and -C(2)H(2)) and high-spin (Mo(2)-C(2)H(4) and -C(2)H(2)) complexes. In the ground state of Mo(1,2)-C(2)H(4) and -C(2)H(2), the metal-center always reacts with the C-C center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a pi-acceptor ligand correlates with a maximum charge transfer from the metal center to the C-C bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the C-C basin. The interaction between Mo(1,2) and C(2)H(4) (or C(2)H(2)) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo(1,2) and NH(3), and the partners are bound by an electrostatic interaction.     

2MgO·2B2O3·MgCl2·14H2O-7.8%H3BO3-H2O体系多温相关系研究

研究了2MgO·2B2O3·MgCl2·14H20在不同温度下的7.8%H3BO3水溶液中的相转化产物及其溶解度.IR,XRD,TG及化学分析表明,相转化产物在0～22℃范围内为MgO·2B2O3·9H20;22～68℃为MgO·2B2O3·7.5H20;68～95℃为MgO·2B2O3·7H20;95～98.8℃为MgO·2B2O3·5H20;100～110℃为MgO·B2O3·3H20;110～120℃为2MgO·B2O3·2H20;120～170℃为2MgO·B2O3·1.5H20;170～200℃为2MgO·B2O3·H20.提出了相转化反应原理.     

New calculations on the ion-molecule processes C2H2(+) + H2 --> C2H3(+) + H and C2H2(+) + H2 --> C2H4+

New high-level quantum chemical calculations have been undertaken to understand the rates and mechanisms of the reactive and associative channels for the reactants C2H2(+) + H2. The reactive channel, which produces C2H3(+) + H, has been shown to be slightly endothermic, confirming earlier calculations at a somewhat lower level and in agreement with some recent experimental work. The associative channel, leading to C2H4+, has been shown to proceed via a transition state with negative energy relative to the reactants, so that association is predicted to be efficient. This result is in conflict with an earlier theoretical study but in agreement with low-temperature experimental measurements.     

Monobridged Si2H4

The rotational spectrum of a new monobridged isomer of Si(2)H(4), denoted here as H(2)Si(H)SiH, has been detected by Fourier transform microwave spectroscopy of a supersonic molecular beam through the discharge products of silane. On the basis of high-level coupled cluster theory, this isomer is calculated to lie only 7 kcalmol above disilene (H(2)SiSiH(2)), the most stable isomeric arrangement of Si(2)H(4), and to be fairly polar, with a calculated dipole moment of mu = 1.14 D. The rotational spectrum of H(2)Si(H)SiH exhibits closely spaced line doubling, characteristic of a molecule undergoing high-frequency inversion. Transition state calculations indicate that inversion probably occurs in two steps: migration of the bridged hydrogen atom to form silylsilylene, H(3)SiSiH, and then internal rotation of the SiH(3) group, followed by the reverse process. The potential energy surface for this type of inversion is quite shallow, with a barrier height of only 2-3 kcalmol. Searches for the rotational lines of silylsilylene, calculated to be of comparable stability to H(2)Si(H)SiH but about five times less polar (mu = 0.23 D), have also been undertaken, so far without success, even though strong lines of H(2)Si(H)SiH have been detected. The favorable energetics and high polarity of monobridged Si(2)H(4) with respect to either disilene or silylsilylene make it a plausible candidate for radioastronomical detection in sources such as IRC + 10216, where comparably large silicon molecules such as SiS, SiC(3), and SiC(4) have already been discovered.     

Vibrational property study of SrGa2H2 and BaGa2H2 by inelastic neutron scattering and first principles calculations

Vibrational properties of the gallium hydrides SrGa2H2 and BaGa2H2 have been investigated by means of inelastic neutron scattering (INS) and first-principles calculations. The compounds contain Ga-H units being part of a two-dimensional polyanionic layer, [(GaH)(GaH)]2-. The INS spectra are composed of dispersed internal Ga-H bending and stretching modes at frequencies above 600 cm(-1) and external lattice modes at frequencies below 220 cm(-1). Frequencies of the internal modes are not susceptible to the metal countercation, indicating a strong integrity of the polyanionic layer as a building unit in the structures of SrGa2H2 and BaGa2H2. The Ga-H stretching modes have frequencies between 1200 and 1400 cm(-1), which is very low compared to molecular gallium hydrides. The weak Ga-H bond in SrGa2H2 and BaGa2H2 is balanced by Sr(Ba)-H interactions.     

Preparation and coordinating properties of {CH2(o-C6H4CH2SbMe2)}2, a novel wide-angle cis-chelating distibine

The unique wide-angle distibine, {CH2(o-C6H4CH2SbMe2)}2, has been prepared indirectly by reaction of Me2SbCl with the di-Grignard formed unexpectedly by coupling of o-C6H4(CH2MgCl)2 in concentrated thf solution, and directly by treatment of the {CH2(o-C6H4CH2MgCl)}2 with Me2SbCl. The very oxygen-sensitive distibine has been characterised by 1H and 13C{1H} NMR spectroscopy and high-resolution EIMS. Oxidation of with Br2 gives the air-stable tetrabromide {CH2(o-C6H4CH2SbMe2Br2)}2. Surprisingly, shows a very strong tendency to function as a cis-chelate, e.g. to Pt(IV) in the complex [PtMe3I], forming an 11-membered ring and providing a stable Pt(IV) stibine complex, the crystal structure of which shows the Sb-Pt-Sb angle to be 95.96(1) degrees. The yellow Pt(II) complex [PtCl2] is obtained from reaction of [PtCl2(MeCN)2] with and IR spectroscopic data and a crystal structure determination confirm the Cl ligands are mutually cis in this species. Reaction of [W(CO)4(piperidine)2] with in refluxing EtOH gives [W(CO)4], the IR spectrum of which shows four nu(CO) bands, also consistent with cis-Sb2 coordination. The cis-chelation is also confirmed by single-crystal X-ray structure determinations of two polymorphs of [W(CO)4].     

微过氧化物酶-11修饰电极对O2和H2O2的电催化还原

运用电化学循环伏安法和旋转圆盘电极技术研究了Ｏ２和Ｈ２Ｏ２在Ｎａｆｉｏｎ膜固定的微过氧化物酶－１１修饰的玻磷（ＭＰ－１１＋Ｍａｆｉｏｎ／Ｇｃ）电极上的电化学还原,结果表明,饰电极 对Ｏ２和Ｈ２Ｏ２的还原均具电催化作用。测定和比较了Ｏ２和Ｈ２Ｏ２在ＭＰ－１１＋Ｎａｆｉｏｎ／ＧＣ的电极上电催化还原反应的一些动力学参数。发现Ｏ２在修饰电极上经历了四电子还原,且还原过程与溶液的ＰＨ值有关。     

Energy density analysis of cluster size dependence of surface-molecule interactions: H2, C2H2, C2H4, and CO adsorption onto Si(100)-(2x1) surface

Adsorption of H2, C2H2, C2H4, and CO onto a Si(100)-(2x1) surface has been treated theoretically using Si(12n - 3)H(8n + 4) (n = 1-4) clusters. The energy density analysis (EDA) proposed by Nakai has been adopted to examine surface-molecule interactions for different cluster sizes. EDA results for the largest model cluster Si45H36 have shown that the adsorption-induced energy density variation in Si atoms decays with distance from the adsorption site. Analysis of this decay, which can be carried out using the EDA technique, is important because it enables verification of the reliability of the model cluster used. In the cases of H2, C2H2, C2H4, and CO adsorption onto the Si(100)-(2x1) surface, it is found that at least a Si21H20 cluster is necessary to treat the surface-molecule interaction with chemical accuracy.