摘要
研究氨基酸型席夫碱金属配合物有助于了解生物体内金属离子-蛋白质间的键合作用，并且可以用来进行生物模拟研究。牛磺酸及牛磺酸缩邻香草醛席夫碱配合物目前未见报道。
本论文工作对牛磺酸及牛磺酸缩邻香草醛席夫碱配合物的研究情况进行了探讨。合成了两个系列四个配合物，其中三个是未见报道的新配合物--配合物（1）、（3）、（4）；另一个为利用不同的试剂、不同的方法合成的别人不能重复的镍配合物--配合物（2）。并对它们的结构进行了解析。通过元素分析，红外光谱和x-射线单晶衍射等手段，研究了金属铜(Ⅱ)离子、镍(Ⅱ)离子与牛磺酸及牛磺酸缩邻香草醛席夫碱形成的三元、四元配合物的结构，并对其中一个牛磺酸螯合物进行了热重-红外联用和量子化学方面的研究。
配合物（1）[Cu(C12H8N2)(NC2H6SO3)(CH3CO2)]·2H2O属三斜晶系，Pī空间群。铜离子的配位多面体为五配位的四方锥形，它是一个四元配合物。牛磺酸以两个配位原子（O1，N1）与铜离子配位，邻菲啰啉以通常的二齿配位提供两个N原子（N2，N3）与铜离子配位，此外，醋酸根也提供了一个配位O原子（O4）参与配位。配合物中，结晶水、未配位磺酸基氧以及未配位的羧基氧之间通过氢键相连，形成三维网状结构。
配合物（2）K3Na[Ni9(NH2CH2CH2SO3)6(Ac)6(H2O)6(OH)6(CO3)2]属菱形晶系，R3c空间群。配合物中，镍离子与镍离子之间没有直接成键，而是通过不多见的μ3-OH-桥连接，每个羟基氧与三个镍离子配位。另外，在笼状配合物中还包裹着两个碳酸根，碳酸根的三个氧都参与了配位。九个镍中只有两种配位环境，配位多面体均为畸变的八面体。
配合物（3）[Ni(C12H8N2)2(C10H11NO5S)]·4H2O属三斜晶系，Pī空间群。牛磺酸缩邻香草醛席夫碱以两个配位原子（O1，N1）与中心镍离子配位，有两个邻菲啰啉参与了配位，每个邻菲啰啉提供两个配位原子。镍离子的配位多面体是畸变的八面体结构，它是一个三元配合物，配合物分子间靠分子间引力、氢键而结合。
配合物（4）{[Cu(C12H8N2)(C10H11NO5S)]·3.25H2O}2属单斜晶系，P2(1)/c空间群。这是一个二聚体，两个铜离子的配位多面体均为五配位的四方锥形。牛磺酸缩邻香草醛席夫碱以三个配位原子（O1，O2，N1）与铜离子配位，邻菲啰啉以两个配位原子（N2，N3）与铜离子配位，配合物分子靠分子间引力结合在一起。
The research on the complexes with amino-acid schiff base and metal is helpful to understanding the bonding action between metal ions and protein in organisms and can be used in the study of biosimulation. So far the complexes with taurine and taurine o-vanillin schiff base have not been reported.
This thesis discuses studies of the complexes with taurine and taurine o-vanillin schiff base. The author has synthesized two series, four complexes, three of them-the complexes(1)、(3)、(4) are new and have not been reported, the complex(2) is a complex with Ni(Ⅱ) ion, synthesized in different chemical agent and in a different way, which others can not repeat. The structure of them has been analysed. By means of single crystal x-ray diffraction, IR Spectrum, and Elemental Analysis, the structure of tribasic, tetrabasic complexes with Ni(Ⅱ)、Cu(Ⅱ) and taurine, taurine o-vanillin schiff base has been studied. In addition, research work on the chelate complex of taurine by TG-IR and quantum chemistry has been done.
The crystal structure of the complex(1) [Cu(C12H8N2)(NC2H6SO3)(CH3CO2)]·2H2O belongs to triclinic system with space group Pī. The coordination polyhedron of copper ion is a five-coordination cone. It is a tetrabasic complex. The Cu(Ⅱ) ion is coordinated by one oxygen atom and one nitrogen atom from the ligand o-phenanthroline, in addition ,the ligand acetate also provides one oxygen atom to coordinate the complex. In the complex, crystaled water, uncoordinated sulfonic oxygen, and uncoordinated carboxylic oxygen are connected by hydrogen bonds so as to form a three dimensional network structure.
The complex(2) K3Na[Ni9(NH2CH2CH2SO3)6(Ac)6(H2O)6(OH)6(CO3)2] crystal structure is rhombohedral system with space group R3c .There are no M-M bonds among nickel and nickel ions in the complex, these ions are connected by the OH- group which is bonded in a μ3 fashion to three nickel ions. In the clathrate complex, it wraps up two CO32- groups of which the three oxygen atoms are bonded. There are two coordination surroundings among nine nickel ions. In the crystal each Ni(Ⅱ) ion is six coordinated to form an octahedral polyhedron.
The complex(3) [Ni(C12H8N2)2(C10H11NO5S)]·4H2O crystal structure is triclinic system with space group Pī. The central Ni(Ⅱ) ion is coordinated by one oxygen atom and one nitrogen atom from the ligand taurine o-vanillin schiff base. There are two o-phenanthroline in the coordination, each providing two coordinated atoms. In the crystal Ni(Ⅱ) ion is six coordinated to form an octahedral polyhedron, it is a tribsic complex. The compound is connected by intermolecular attractive force and hydrogen bonds.
The complex(4) {[Cu(C12H8N2)(C10H11NO5S)]·3.25H2O}2 belongs to monoclinic system with space group P2(1) /c. It is a bipolymer. The coordination polyhedron of copper ion is a five-coordination tetragonal cone. The Cu(Ⅱ) ion is coordinated by two oxygen atoms and one nitrogen atom from the ligand taurine o-vanillin schiff base and two nitrogen atoms from the ligand o-phenanthroline. The compound is connected by intermolecular attractive force.
引文
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