α-氰基-P-X苯基乙酸乙酯的[Cu^2+(OH^-)TMEDA]2Cl2-催化氧化偶联反应机理

在[Cu~(2+)(OH~-)TMEDA]_2Cl_@~-催化下(TMEDA为N,N,N′,N′-四甲基乙二胺),α-氰基-p-X苯基乙酸乙酯(X=OCH_3,CH_3,Gl,H和NO_2)经氧化偶联反应,获得高产率的二聚体。产物中meso异构体的含量均大于dl异构体的含量。IR,~1HNMR和EPR对反应过程研究结果表明,反应机理为底物以CN取代催化剂中的OH~-,生成反应中间体配合物,OH~-夺取底物的α-H,产生相应的碳负离子,碳负离子向Cu~(2+)单电子转移生成自由基,自由基偶合而生成产物。氧将Gu~+氧化为Cu~(2+),使反应继续进行。     

过渡金属钼钒砷杂多化合物的合成与TPR,TPD研究

Seven transition metal molybdovanadoarsenic heteropoly compounds have been synthesized and characterized using IR, UV, TG-DTA, pH potential titration techniques. The molecular formulae of these compounds are pro-posed to be H_xM_yAsMO₁₀V₂O₄₀·zH₂O(x=1～3, y=1,2, M=Cr, Mn, Fe, Co, Ni, Cu, Zn).They are all keggin structure. Surface nature of these compounds have been investigated by temperature programmed desorption and temperature programmed reduction techniques. NH₃-TPD results show that in TPD profiles of the compounds there are two desorption peaks corresponding to weak acid sites of desorption, respectively. Desorbing activativon energy and preexponential factor of weak acid site of desorption for compounds have been calculated. H₂-TPR re-sults show that introducting transtion metal to molybdovanarsenic acid, the reduction peak temperatures of H₂-TPR shift regularly with increasing d electron numbers of transition metals. In addition, Zn and Cu heteropoly com-pounds have yet apparent effect of hydrogen spill over.     

聚苯并咪唑金属复合物的X-射线光电子能谱(XPS)研究

本文报道以聚苯并咪唑(PBI)与某些过渡金属卤化物所形成的金属复合物的XPS研究,由反映在金属复合物N_(1s)和C_(1s)振起(Shake-up)伴峰的消失,反映在PBI中N_(1s)双峰变为复合物中的具有高结合能的单峰以及与其复合金属离子结合能的降低,这就从施受两个侧面确证金属复合物的形成。XPS结果也说明在金属复合物的制备中,不同溶剂条件所制得的复合物在硅氢加成中活性丧失归结於溶剂导致的金属离子的还原。     

聚（2,5—二甲氧基对苯乙炔）的可溶性前聚物合成及表征

研究了合成聚（２，４－二甲氧基对苯乙炔）的有机可溶性前聚物的反应条件与单体转化率和前聚物产率的关系。实验结果表明：ＮａＯＨ是聚合反应的有效引发剂，适宜的反应条件为：单体与ＮａＯＨ摩尔比为１：１，单体浓度０．０５－０．２ｍｏｌ／Ｌ，聚合时间２ｈ，温度低５℃，正己烷、石油醚作为有机提取剂可有效提高前聚物产率。用ＩＲ、ＵＶ－Ｖｉｓ＇＾ＨＮＭＲ，ＴＧＡ和 ＤＳＣ对前聚物进行了表征。     

双邻苯二酚锑二甲基羟乙铵的晶体结构

含锑配合物是治疗血吸虫病、肿瘤等的常用药物,我们曾对双邻苯二酚锑二乙基羟乙胺进行了晶体结构测定,本文简要报导双邻苯二酚锑二甲基羟乙胺的结构.锑化合物的制法与其二乙基羟乙铵衍生物类似.产物为淡黄色晶体,它在水溶液中长时间放置会变成紫黑色,因此,制得的晶体须立即用丙酮溶解进行重结晶.晶体的密度为1.667g/cm~3.按C_(16)H_(20)O_5NSb的元素分析结果(％)如下:Sb 28.3(28.5),C 43.9(44.9),N 3.3(3.3),H 4.7(4.7).括号内为理论值.     

二维网状铜(Ⅱ)配合物的合成及晶体结构表征

A Cu(Ⅱ) complex [Cu(L)_1.5(OSO₃)]·3H₂O (1) [L=1,4-bis(imidazol-1-yl)benzene] was synthesized by reaction of ligand L with CuSO₄·5H₂O using solvothermal method and its structure was determined by X-ray crystal structure analysis. The structure indicates that the complex crystallizes in triclinic, space group P1 with a=0.948 8(2), b=1.078 5(2), c=1.108 4(2) nm, α=74.820(2), β=81.331(2), γ=72.638(2)°, V=1.041 5(3) nm³, Z=2, D_calc=1.687 g·cm^-3, F(000)=544, μ=1.205 cm^-1, the final R=0.062 3 and wR=0.132 8. The Cu(Ⅱ) atom has distorted square-pyramidal environment with a N₃O₂ donor set. Each L ligand links two Cu(Ⅱ) atoms using its imidazole groups to form an infinite one-dimensional (1D) ladder-like chain, which further linked by SO₄^2- to form a two-dimensional (2D) network structure. The 2D sheets are further connected by C-H…O hydrogen bonds to give a three-dimensional (3D) structure. CCDC: 650388.     

希土Eu(Ⅲ)与2-丙酰-茚满二酮-1,3的二元、三元配合物的合成、表征及发光性能研究

合成2-丙酰-茚满二酮-1,3及其Eu(Ⅲ)的二元、三元固态配合物,经化学分析、元素分析确定了配合物的化学组成,通过红外光谱、紫外光谱进行表征,用配合物的荧光光谱和配体低温磷光光谱分析了配合物的荧光强度和能有效发光的原因.