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取代四苯基卟啉锌与金属Schiff碱配合物轴向配位反应的热力学研究
引用本文:陈红卫,朱志昂,阮文娟,张智慧,陈正华,陈荣悌. 取代四苯基卟啉锌与金属Schiff碱配合物轴向配位反应的热力学研究[J]. 化学学报, 1997, 55(4): 380-385
作者姓名:陈红卫  朱志昂  阮文娟  张智慧  陈正华  陈荣悌
作者单位:南开大学化学系
基金项目:国家自然科学基金,天津市自然科学基金,南开大学吸附分离功能高分子材料国家重点试验室等资助的课题.
摘    要:用紫外-可见光谱和Rose-Drago数据处理方法对多种新型空间不对称含咪唑基团金属Schiff碱配合物与取代四苯基卟啉锌[ZnT(p-X)PP]轴向配位反应平衡常数进行了测量。研究了配体和卟啉上取代基、反应温度等因素对平衡常数的影响, 发现各配体与锌卟啉配位反应的平衡常数与卟啉环上取代基的Hammett参数之间存在线性自由能关系。在二氯甲烷中, 利用温度系数法测量了反应体系的△rHm^○和△rsm^○。

关 键 词:紫外分光光度法  锌络合物  平衡常数  席夫碱  卟啉  络合反应  

Thermodynamic study of coordination reactions of parasubstituted zinc tetraphenylporphyrins with metallic Schiff base complexes
CHEN HONGWEI,ZHU ZHIANG,RUAN WENJUAN,ZHANG ZHIHUI,CHEN ZHENGHUA,CHEN RONGTI. Thermodynamic study of coordination reactions of parasubstituted zinc tetraphenylporphyrins with metallic Schiff base complexes[J]. Acta Chimica Sinica, 1997, 55(4): 380-385
Authors:CHEN HONGWEI  ZHU ZHIANG  RUAN WENJUAN  ZHANG ZHIHUI  CHEN ZHENGHUA  CHEN RONGTI
Abstract:Equilibrium constants for reactions of ZnT (p-X)PP (parasubstituted zinc tetraphenylporphyrins) with ligands of Schiff base complex in CH2Cl2 and several other solvents have been measured by visible spectral techniques, and determined by the method of Rose-Drago. Electronic effects in metalloporphyrins and effects of ligands, temperature and solvents were researched. It was found that the equilibrium constants for reactions of ZnT (p-X)PP with ligands follow Hammett equation. The enthalpies and the entropies of reactions were obtained from the plots of lnK^○ vs. 1/T.
Keywords:ULTRAVIOLET SPECTROPHOTOMETRY  ZINC COMPLEX  EQUILIBRIUM CONSTANT  SCHIFF BASE  PORPHYRIN  COMPLEX REACTION
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