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化学学报
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化学学报 ›› 1997, Vol. 55 ›› Issue (4): 380-385. 上一篇    下一篇

研究论文

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

陈红卫;朱志昂;阮文娟;张智慧;陈正华;陈荣悌   

  1. 南开大学化学系
  • 发布日期:1997-04-15

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   

  • Published:1997-04-15

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469

被引次数

2

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

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.

Key words: ULTRAVIOLET SPECTROPHOTOMETRY, ZINC COMPLEX, EQUILIBRIUM CONSTANT, SCHIFF BASE, PORPHYRIN, COMPLEX REACTION

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