含疏水基的大环金属配合物的合成、结构和性质研究-无机化学专业论文.docx

2004届中山大学硕士学位论文 2004届中山大学硕士学位论文 彭青 (II)配合物而言，结果相反，疏水基团的引入对锌(II)配合物的K(ML)和pKa基本 上无影响，但与B．环糊精的包合却使得锌配合物的K(ML)值降低，而pKa值升高。 这一结果很可能是由于环糊精上．CH20H的氧原子与Zn(II)配位造成，而所测的 实验pKa值实际上是环糊精上．CH20H的pKa值。 5．另外在本科毕业论文的工作基础上合成了配体4，5．二羧酸咪唑 (DCBI)，并得到Mn(II)配合物，配合物Mn(DCBI)2∞o)2的结构己通过X．射 线晶体结构检测仪检出。两个DCBI配体与锰原子在同一水平面上，锰原子同时 与两个相同配体DCBI上的两个眯唑氮原子和两个羧酸根上的两个氧原子配位， 轴向上锰原子分别与两个水分子上的氧原子配位，形成扭曲的八面体结构。配体 的两个羧酸根上的氧原子形成了分子内氢键，配位水与相邻分子上的羧酸根上的 氧原子形成分子间氢键，配体DCBI上未配位的氮原子也与相邻分子上羧酸根的 未配位氧原子形成分子间氢键。这些分子间氢键的形成构筑了该化合物的三维结 构。 关键词：碳酸酐酶模型，四氮杂环，疏水环境，铜配合物，锌配合物 Ⅱ !!竺旦±坐查堂堡圭堂丝塑茎——一—————————————————!!二生Synthesis，Characterization !!竺旦±坐查堂堡圭堂丝塑茎——一—————————————————!!二生 Synthesis，Characterization and Properties of the New Metal Complexes ofp——isopropylbenzyl Cyclen Major：Inorganic Chemistry Name：Peng Qing Supervisor：Dr．Mao Zong-Wan ABSTRACT The study on the structure—function relationship of the carbonic anhydrase has been one of the interesting research field of biochemistry,inorganic chemistry and computational chemistry．In order to consmact model compounds with Nologic environment of the active center of the enzyme，we reconstructed the present best model，that is，adding some active functiomd groups and hydrophobic environment on basis of keepmg initial active coordhmted structure of the metal ion．In another word， we did some probing work how to construct new mDdel for the carbonic anhydrase in the past three years．The main contribution ofthe thesis includes following parts： 1．One ligand and their zinc(if)and copper(II)complexes had been synthesized and characterized by 1H NMR,IR，MS and EA．They are[CuL(H20)](C104)2’H20 and [ZnL(MeCN)](C104)2 respectively,in which L=1巾一isopropylbenzyl-1，4，7，10一tetraazacyclododecane； 2．The zinc(II)and copper(Ⅱ)complexes with ligand L had been characterized by X—ray technique．It showed that a distorted square pyramidal Zn-N5·coordinate structure with four nitrogens of the cyclen moiety and one nitrogen of acetonitrile for 【ZnL(MeCN)](C104)2．For the copper(II)complex[CuL(n20)](CL04)2。H