合成物

This thesis consists of three main parts of the research work on the syntheses, structures and reactivities of the olefin-coordinated transition metal carbene and carbyne complexes. In chapter 1, on the basis of our previous research works on the reacitivites of the cationic carbyne complexes of transition metals with metalcarbonyl anions, we explored the reactions of the cationic carbyne complexes of manganese (1) and rhenium (2) with polymetalcarbonyl anions, and developed a new method for the preparations of heternuclear trimetal bridging carbyne complexes.

本论文对烯烃配位的过渡金属卡宾和卡拜络合物的合成、结构和反应性能进行了研究，主要进行了如下三方面的工作：第一章在本小组过去的研究基础上，进一步考察锰和铼的阳离子卡拜络合物1和2与羰基金属阴离子化合物的反应，用来合成异核多金属桥卡拜络合物，发展合成多金属桥卡拜络合物的新方法和新路线。

It is demonstrated that the chiral quaternary ammonium salts catalysts exhibit promising catalytic properties for the substrate. Part III: The synthesis and the characterizing of the macroporous aminomethyl resin-supported cinchona alkaloid complexes and the study on its catalytic properties The part consists of two subsections. the macroporous aminomethyl resin -supported cinchona alkaloid complexes were synthesized by the stuff (cinchonine, quinine and macroporous aminomethyl resin). Their structures were characterized by means of elemental analysis, XPS, TG/DTA; the chiral polymer-supported complexes were first used as catalysts for the reduction of ketones. Their catalytic properties for the reduction processes were investigated. The comparison of the products e.e., the conversion of the substrate among different reduction processes was employed with determined by HPLC. The effects of the time, the temperature, the ratio of catalyst to substrate, reaction solvent as well as the recycle times were also discussed.

第三章聚-4-氨甲基苯乙烯负载金鸡纳碱金属络合物的合成与表征及其不对称催化性能研究本章分为两节，以辛可宁和奎宁及聚-4-氨甲基苯乙烯为原料，合成了4种聚-4-氨甲基苯乙烯负载金鸡纳碱络合物催化剂，并对它们的结构用元素分析、X-射线光电子能谱、TG/DTA等几种测试手段进行了表征；首次将所合成的手性高分子负载的金属络合物用于催化芳香酮不对称还原反应，详细研究了所得的手性高分子负载的金属络合物对不同底物的催化性能，用HPLC等分析手段定量检测了还原过程的底物转化率及其产物对映异构体选择性，并考察了反应时间、反应温度、催化剂和底物投料比、反应溶剂和循环次数对催化性能的影响。

This paper contains three parts: 1 Synthesis of novel titanium complexes; 2 Polymerization behaviors of alkoxyl substituted Cp Titanocenes as catalysts for styrene syndiotactic polymerization; 3 Polymerization behaviors of alkenyl substituted Cp Lanthanocenes as Methyl Methacrylate polymerization catalysts.

中文题名新型茂钛、噁唑啉钛络合物的合成、表征以及茂钛、茂稀土络合物催化性能的研究副题名外文题名 Synthesis，characterization of novel Cp，oxazoline titanium complexes and polymerization behaviors of titanocenes and lanthanocenes 论文作者张浩导师钱延龙黄吉玲学科专业应用化学研究领域\研究方向金属有机与均相催化学位级别博士学位授予单位华东理工大学学位授予日期2003 论文页码总数148页关键词金属有机化学稀土络合物噁唑啉类钛络合物茂钛络合物馆藏号BSLW /2003 /O627 /27 本论文包括三部分内容：1）有机金属钛络合物的合成；2）烷氧基取代茂钛络合物催化苯乙烯间规聚合的研究；3）烯基取代茂稀土络合物催化甲基丙烯酸甲酯聚合的研究。

The invention is characterized in that the molecule of the polymer adsorption material has a structure in formula I: in the formula, R is selected from the natural polysaccharides with amino groups and hydroxyls and the derivatives thereof or the chemosynthetic polymers, the molecular weight of which is from 6 KD to 500 KD; X is selected from a C0 to C6 paraffinic chain with O atoms, N atoms or OH groups; R1, R2 and R3 are selected from a C1 to C4 alkyl group.

生物医学材料领域中的水溶性阳离子多聚物吸附材料及其应用，包括采用带有氨基或羟基的天然多糖及其衍生物或者化学合成多聚物季铵化反应合成，其特征在于该多聚物吸附材料分子具有式的结构：式中，R选自粘均分子量范围为6KD～500KD的带有氨基或羟基的天然多糖及其衍生物或者化学合成多聚物；X选自含有O原子、N原子或者OH基团的C 0 ～C 6 烷链；R 1 、R 2 、R 3 选自C 1 ～C 4 的烷基。

In this thesis, a series of complexes based on aromatic multicarboxylic acids have been successfully synthesized in solutions or under hydrothermal conditions. Their structure and properties are investigated.(1) Eight complex compounds have been synthesized and characterized by X-ray single crystal diffractive technology: The eight complexes are listed as following: [Cu242] complex 1 [Cd22(H2O)4]·4H2O complex 2 [Co(H2btc)(H2O)3] complex 3 [Co2(H2O)2]·H2O complex 4 [Ni22(H2O)4] complex 5 [Cu22(H2O)4] complex 6 [Co(H2biim)2(H2O)2](H2btc) complex 7 [Zn(H2biim)2(H2O)2](H2btc) complex 8 The structure of complex 1 is dinuclear complex resulted from weak interactions（0-D chain）; complex 2 is 1-D chain stucture result from interactions of water molecules; complex 3、4、5、6 are coordination polymers using hydrothermal synthses, where the first kind ligand is H4btc, the second kind ligand is phen and Co2+、Ni2+、Cu2+ as center ions, respectively. While the coordination enviroment of Co2+ is the same in complex 3, the coordination geometries around the Co atoms in complex 4 are obviously different because of the different reaction conditions. In complex 4, the 1-D chains are connected into 2-D layer through carboxy groups of ligand H4btc. The structures of complex 5、6 are 1-D chain stucture result from interactions of carboxy groups in ligand H4btc. Complex 7、8 are homeomorphy compounds. Either of them are linked to the 3-D chains through intermolecular hydrogen bonds. Each H4btc lose two protons and H2btc2- acts as negative electron balance.

合成了8个结构新颖的配合物，并用X-射线单晶结构分析方法确定了晶体结构，分别为： [Cu242] 配合物1 [Cd22(H2O)4]·4H2O 配合物2 [Co(H2btc)(H2O)3] 配合物3 [Co2(H2O)2]·H2O 配合物4 [Ni22(H2O)4] 配合物5 [Cu22(H2O)4] 配合物6 [Co(H2biim)2(H2O)2](H2btc)配合物7 [Zn(H2biim)2(H2O)2](H2btc)配合物8 配合物1是一个依靠弱作用连接的双核铜结构；配合物2借助水分子形成一维链状结构；配合物3、4、5、6是以H4btc为第一配体、phen为第二配体，通过水热法合成的配合物，其中，Co2+、Ni2+、Cu2+为中心离子；配合物3中的二价钴离子具有相同的配位环境，不同反应条件下得到的配合物4中的二价钴离子存在不同的配位环境，在配合物4中，一维链通过H4btc上的羧基形成一个二维层结构；配合物5、6是借助H4btc上的羧基形成的一维链状结构；配合物7、8属于异质同晶结构，它们的分子通过分子间氢键形成三维网状结构，H4btc上的羧基失去2个质子，作为一个二价负离子起到电荷平衡作用。

In this study aldylencdithiomethylene Malonic acid acts as the main coordination agents and compound iron ion have been synthesized by the means of solution, As a result ,the 1D polymer is obtained.

本论文采用常规的溶液合成方法，首先设计合成了一个以含有二硫缩烯酮结构的丙二酸类配体和过渡金属铁离子的单核配合物，再以此单核配合物作为配体设计合成了三个异多核配合物和配位聚合物。

Finally, the cytotoxic and antibacterial activities of the oxamido-bridged binuclear complexes were studied in vitro.. This dissertation consists of three sections as follows:1. The crystal structure of a oxamide dinitrate,(1) [H_4dmaeoxd](NO_3)_2 H_2dmaeoxd = N,N\'-bis[2-ethyloxamide, has been obtained. The diversity of complexes with different structures is carried out by successful synthetic strategy of controlling species of metal ions, counter anions, pH values and solvents in the course of synthesis. Four dinuclear complexes bridged by trans-dmaeoxd2-: [Cu_2_2](ClO_4)_2 (2), [Cu_2_2](ClO_4)_2 (3),、[Cu_2(Me_2phen)_2](ClO_4)_2 (4), [Cu_2_2(H_2O)_2] (5); Four dinuclear complexes bridged by cis-dmaeoxd2-: [NiNi_2](ClO_4)_2 (6), [CuNi_2](ClO_4)_2·2CH_3OH (7), [CuZn_2]-(ClO_4)_2·2H_2O (8), [Cu(H_2O)Ni_2](ClO_4)_2.0.5CH_3OH (9); three 1-D polynuclear complexes: [Cu_2]_n·nH_2O (10), [Cu_2(H_2O)_2-]_n·4nH_2O (11), [Cu_2(H_2O)]_n(NO_3)_n·2nH_2O (12); one 2-D polynuclear complex,[Cu_6_3(μ_3-OH)_2(H_2O)_2]_n(ClO_4)_(4n).2nH_2O (13); the others: [VO(H_2O)]·2H_2O (14), [Zn_2_4](ClO_4)_2·H_2O (15), [Cu_2]·2DCM (16) have been synthesized and characterized by X-ray single crystal diffraction, elemental analysis, IR spectra.

本论文主要包括以下三部分：一、合成得到了一个草酰胺配体硝酸盐的单晶结构，[H_4dmaeoxd](NO_3)_2 (1)；通过调控金属离子的种类、端基配体、抗衡阴离子、溶剂、pH值等条件定向合成了四个反式草酰胺桥联双核铜配合物：[Cu_2_2](ClO_4)_2 (2)、[Cu_2_2](ClO_4)_2 (3)、、[Cu_2(Me_2phen)_2](ClO_4)_2 (4)、[Cu_2_2(H_2O)_2] (5)；四个顺式草酰胺桥联同/异双核配合物：[NiNi_2](ClO_4)_2 (6)、[CuNi_2](ClO_4)_2·2CH_3OH (7)、[CuZn_2]-(ClO_4)_2·2H_2O (8)、[Cu(H_2O)Ni_2](ClO_4)_2.0.5CH_3OH (9)；三个一维聚合物： [Cu_2]_n·nH_2O (10)、[Cu_2(H_2O)_2-]_n·4nH_2O (11)、[Cu_2(H_2O)]_n(NO_3)_n·2nH_2O (12)；一个二维聚合物： [Cu_6_3(μ_3-OH)_2(H_2O)_2]_n(ClO_4)_(4n)。2nH_2O (13)；单核钒配合物[VO(H_2O)]·2H_2O (14)、草酸根桥联双核锌配合物[Zn_2_4](ClO_4)_2·H_2O (15)、美洛西康铜配合物[Cu_2]·2DCM (16)，利用元素分析、摩尔电导、红外光谱、电子光谱和单晶X-射线衍射对上述所得化合物进行了结构表征，探讨了结构影响因素，并研究了其超分子结构。

Picolinic acid∶Eu3+ complex synthesized in aqueous solution was determined by DTATG, ultraviolet absorption spectra and infrared spectra.

通过差热－热失重、红外光谱和紫外光谱等测试手段，对溶液中合成的吡啶－2－羧酸∶Eu3＋配合物进行了表征，并且通过原位合成方法在SiO2凝胶中合成了吡啶－2－羧酸∶Eu3＋配合物，与溶液中合成的吡啶－2－羧酸∶Eu3＋配合物进行了对比。

The molecular designs and synthesis of triarylamine-based picolinic acid derivatives used as ancillary ligands, and their cyclometalated iridium complexes used as red-and green-emitters, as well as optoelectronics properites of these compounds were investigated in order to solve current problems of organic/polymeric electroluminescent materials and devices.

本论文针对目前有机/聚合物电致磷光材料和器件存在的问题，开展了新型三芳胺吡啶羧酸类辅助配体及其红光和绿光环金属铱配合物电致磷光材料的分子设计、合成和光电性能研究，主要包括：(1)设计、合成了三种新型的三芳胺吡啶羧酸类双齿阴离子型辅助配体；(2)以三芳胺吡啶羧酸衍生物作为双齿阴离子型辅助配体，合成得到了两个系列的红光和绿光环金属铱配合物；(3)研究了三芳胺吡啶羧酸类辅助配体分子结构对环金属配合物的紫外吸收和光致发光性能的影响；(4)以环金属配合物为客体，聚芴和恶二唑衍生物为主体，制作了聚合物电磷光器件，研究了含三芳胺吡啶羧酸类辅助配体、环金属配合物客体材料和聚合物主体材料等分子结构对电致发光性能的影响。

The main contributions of this thesis are:(1) Seven mononuclear complexes of tetradentate ligand NTB have been obtained using N〓 or SCN〓 as the additional ligand;(2) Seventeen binuclear complexes of Fe , Zn , Co , Cu have been designed and the complexes of Co , Cu exhibit antiferromagnetic properties;(3) Changing the bridged-ligand such as PO〓, CO〓, o-phth, mai, Ag (CN 〓, Au 〓, etc , fourteen tetranuclear complexes of polypridine ligand have been synthesized;(4) Two antiferromagnetic 1D chain complexes of KH〓pdc ligand have been prepared from hydrothermal reactions; in addition, one ferromagnetic 1D chain copper complex of tpdp which is bridged by oxalate has been obtained.

本论文的主要贡献为：(1)合成了配体NTB的七个新型单核配合物；(2)合成了十七个铁、锌、钴及铜系列混桥双核配合物，其中双核钴和双核铜配合物为反铁磁偶合；(3)选用多吡啶配体tpdp和TPA，改变桥联配体，合成了十个四核配合物；(4)选择配体KH〓pdc，采用水热合成方法得到了反铁磁性一维链状锰、铜配合物；以草酸根为桥联配体，合成了配体tpdp的一维链状铜配合物，该化合物为铁磁偶合，文献较少报道。

As she looked at Warrington's manly face, and dark, melancholy eyes, she had settled in her mind that he must have been the victim of an unhappy attachment.

每逢看到沃林顿那刚毅的脸，那乌黑、忧郁的眼睛，她便会相信，他一定作过不幸的爱情的受害者。

Maybe they'll disappear into a pothole.

也许他们将在壶穴里消失