高等学校化学学报

高等学校化学学报 ›› 1997, Vol. 18 ›› Issue (10): 1571.

• 论文 •    下一篇

非对称取代卟啉钴(Ⅱ)轴向配位反应的热力学研究

邵迎, 朱志昂, 阮文娟, 杨绍英, 田建华, 马刚, 张智慧, 陈荣悌   

  1. 南开大学化学系, 天津 300071
  • 收稿日期:1996-10-28 出版日期:1997-10-24 发布日期:1997-10-24
  • 通讯作者: 朱志昂
  • 作者简介:邵迎, 女, 40岁, 天津医科大学药学院讲师, 南开大学访问学者
  • 基金资助:

    国家自然科学基金;北京分子动态及稳态结构实验室资助;天津医科大学科学研究基金

A Study of Thermodynamic in Axial Coordination Reaction of Unsymmetrical Derivatives of Tetraphenylporphyrinatpcobalt(Ⅱ)

SHAO Ying, ZHU Zhi-Aug, RUAN Wen-Juan, YANG Shao-Ying, TIAN Jian-Hua, MA Gang, ZHANG Zhi-Hui, CHEN Rong-Ti   

  1. Department Of Chemistry, Nankai University, Tianjin 300071
  • Received:1996-10-28 Online:1997-10-24 Published:1997-10-24

PDF (PC)

被引次数

24

摘要： 合成了非对称对位取代叶啉钻(Ⅱ)[5－(4-乙酰胺基苯基-－10,15,20－三(4－甲基苯基)足啉钴钻(Ⅱ)].用分光光度法测量了该体系与一系列含咪唑基配体[2－甲基咪唑(2－MeIm)、N－甲基咪唑(N－MeIm)、2-乙基-4-甲基咪唑(EMIm)、克霉唑(GMZ)］轴向配位反应的平衡常数.研究结果表明,配体的尺寸及取代基的位置将对轴向配合物的稳定性产生影响,其平衡常数呈现KGMZ＞KN-MeIm＞K2-MeIm＞KEMIm的趋势.在对称及非对称体系中,△H与T△S间均存在线性关系.有利的焓变补偿了不利的熵变,熵焓作为一种补偿关系贡献于配合物的稳定性.

关键词: 5－(4-乙酰胺基苯基)－10, 15, 20-三(4-甲基苯基)卟啉钴(Ⅱ), 轴向配位反应, 平衡常数, 空间位阻, 熵焓补偿

Abstract: 5-(4-Acetamidophenyl)-10,15, 20-tris (4-methylphenyl) porphyrinatocobalt (Ⅱ)was synthesized. By means of spectrophotometer technique, the equilibrium constants of theaxial coordination reaction were measured between this system and a series of imedazole lig-ands (2-Melm, N-Melm, EMIm, GMZ) which possess different steric hindrances. Theresults show that the size and the position of the substituting group on a ligand influence thestability of the axial coordinative product, and the equilibrium constants appear in the orderKGMz>KN-Mclm ＞K2-Mclm＞K2-Mclm＞KEMlm Alinear relationship was observed between △Hand T△Sinboth the symmetrical and unsymmetrical systems. The favorable enthalpy changecompensates the unfavorable entropy change and the compensatory enthalpy- entropy relationshipcontributes to the stability of complexes.

Key words: 5-(4-Acetamidophenyl)-10,15,20-tris(4-methylphenyl)porphyrinatocobalt(Ⅱ), Axial coordination reaction, Equilibrium constants, Steric hindrance, Enthalpy-entropycompensation

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