高等学校化学学报

高等学校化学学报 ›› 1989, Vol. 10 ›› Issue (10): 1030.

• 研究论文 • 上一篇    下一篇

对位取代四苯基卟啉铁(Ⅲ)的轴向配位快速反应动力学研究

朱志昂, 马玉新, 陈荣悌   

  1. 南开大学化学系
  • 收稿日期:1988-03-19 出版日期:1989-10-24 发布日期:1989-10-24
  • 通讯作者: 朱志昂

Kinetic Study of Axial Coordination of Para-Substituted (Tetraphenylporphinato) Iron(Ⅲ) Chloride

Zhu Zhi'ang, Ma Yuxin, Chen Rongti   

  1. Department of Chemistry, Nankai University, Tianjin
  • Received:1988-03-19 Online:1989-10-24 Published:1989-10-24

PDF (PC)

被引次数

14

摘要： 用UnionGikenRA-401停流分光光度计对丙酮溶剂中咪唑(Im)与对位取代四苯基卟啉铁(Ⅲ)(Fe(p-X)TPPClX=Cl,H,CH3,OCH3)的轴向配位快速反应动力学进行了研究.提出了反应机理.以CA-033E微机对实验数据进行处理,得到似平衡步的平衡常数K和速控步的速率常数k,并算出了似平衡步的△H?、△S?以及速控步活化参数△H≠、△S≠.发现△H、△S、△H≠、AS≠、InK、Ink分别与Hammett取代常数σ呈直线关系;△H≠和△S≠存在等动力学关系.

关键词: 对位取代四苯基卟啉铁(Ⅲ), 咪唑, 停流法, 反应机理, 等动力学关系

Abstract: Akinetic study is reported for the axial coordination of imidazole(Im).with para-substituted (tetraphenylporphinato)-iron(Ⅲ) chloride [Fe(p-X)TPPCl; X=Cl, H, CH3, OCH3] in acetone by means of Union Giken RA-401 stopped-folw spectrophotometer.The mechanism is postulated as follows:(这里有图片19891013-1030-1.gif)The experimental data were treated with CA-033Emicro computer.The equilibrium constant (K) of the preequilibrium step(l) and the rate constant(k) of the rate determining step(2) were obtained.The standard enthalpy △H?and standard entropy △S?of step (1), and the activation parameters △Hand △S≠of step (2) were calculated.It was found that linear relationships exists between the following pairs : △H?and the Hammett constant δ; △S?and δ ; △H≠and δ ; △S≠and δ; lnKand δ; lnk and δ.The isokinetic relationship between △H≠and △S≠was also found.

Key words: Para-substituted (Tetraphenylporphinato) iron (Ⅲ) chloride, Imidazole, Stopped-flow method, Reaction mechanism, Isokinetic relationship

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