六氮杂三十元大环双核铜配合物的合成及其水解动力学性质  

Synthesis and hydrolysis kinetic properties by a 30-membered hexaaza macrocyclic copper(Ⅱ) complex

作　　者：刘捷[1] 郑玉娟[1] 

机构地区：[1]河南工业大学化学化工学院,河南郑州450001

出　　处：《河南工程学院学报（自然科学版）》2016年第1期27-32,共6页Journal of Henan University of Engineering：Natural Science Edition

基　　金：河南省自然科学基金(2011A150008)

摘　　要：利用对苯二甲醛和二丙烯三胺制备了一个三十元六氮杂大环配体L(L=3,7,11,18,22,26-hexaazatricyclo[26.2.2.213,16]tetratriaconta-1(30),13,15,28,31,33-hexaene),合成了一个新颖的双核铜配合物[Cu_2L](CO_3)_2,用X-单晶衍射分析技术表征了其结构:Cu(Ⅱ)与环上的3个氮原子及来自CO32-上的2个氧原子配位,分别形成配位构型不同的变形四方锥构型和三角双锥构型,采用紫外-可见分光光度法研究了配合物催化p-硝基苯酚醋酸酯(NA)的水解动力学性质.结果表明,催化水解速率对底物NA及配合物的浓度均呈一级反应且催化水解速率受酸碱平衡控制,当pH值=9.00时,水解速率常数为0.034 mol/s,推测其催化机制可能为Lewis acid机制.A new 30-membered hexaaza macrocyclic dinuclear copper（ Ⅱ） complex [Cu2L]（ CO3）2（ L = 3,7,11,18,22,26-hexaazatricyclo[26. 2. 2. 213,16]tetratriaconta-1（ 30）,13,15,28,31,33-hexaene） has been synthesized by condensation of 1,4-phthalaldenhyde and dipropylenetriamine. The results of the X-ray single crystal diffraction analysis technique showed that the copper（ Ⅱ）ion was coordinated to three nitrogen atoms from the macrocyclic ligand and two oxygen atoms from CO32-anion,forming a distorted square pyramidal geometry and a distorted trigonal bipyramidal geometry,respectively. The kinetic properties of catalytic hydrolysis of p-nitrophenyl acetate were investigated by UV-Vis spectroscopy. It turned out that the rate equationof catalytic hydrolysis to the concentration of p-nitrophenyl acetate belongs to the first order reaction,so does to the concentration of the complex. The hydrolysis process was controlled by the acid-base equilibrium. The hydrolysis rate constant of the complex was 0. 034 mol / s at p H = 9. 00. The possible hydrolysis mechanism was suggested.

关 键 词：三十元大环双核铜配合物 晶体结构 p-硝基苯酚醋酸酯 催化水解动力学 

分 类 号：O643.12[理学—物理化学] Q556[理学—化学]