金属离子与卟啉的嵌入反应动力学研究(Ⅳ)──乳酸缓冲体系中四吡啶基卟啉衍生物与铜(Ⅱ)的配位反应

高等学校化学学报 ›› 1994, Vol. 15 ›› Issue (4): 565.

金属离子与卟啉的嵌入反应动力学研究(Ⅳ)──乳酸缓冲体系中四吡啶基卟啉衍生物与铜(Ⅱ)的配位反应

潘志权, 任建国, 秦子斌

1. 武汉大学化学系, 武汉, 430072;
2. 南京大学配位化学国家重点实验室

收稿日期:1993-05-10 修回日期:1993-10-10 出版日期:1994-04-24 发布日期:1994-04-24
通讯作者: 潘志权,男,35岁,硕士,现为武汉化工学院讲师.
作者简介:潘志权,男,35岁,硕士,现为武汉化工学院讲师.
基金资助:
国家自然科学基金

Studies on Kinetics of Incorporation of Metal Ion Porpyrin(Ⅳ)──Coordination Reaction of TPyP Derivatives with Cu²⁺ in Lactic Acid Buffer System

PAN Zhi-Quan, REN Jian-Guo, QIN Zi-Bin

Department of Chemistry, Wuhan Univcrsity, Wuhan, 430072

Received:1993-05-10 Revised:1993-10-10 Online:1994-04-24 Published:1994-04-24

摘要/Abstract

摘要： 研究了在35±0.1℃、离子强度0.5mol/L(KCI)下,乳酸根催化Cu²⁺离子嵌入溴化间-四(N-乙酸甲酯基-3-吡啶基)卟啉和溴化间-四(N-氰乙基-3-吡啶基)卟啉的反应动力学。根据催化剂浓度、溶液的pH值与反应速率间的关系,得到Cu²⁺离子嵌入该类卟啉的反应动力学方程。实验结果表明,该类反应遵循负离子催化卟啉变形机理,变形的卟啉及其与乳酸根离子的缔合物为可能的活性中间体。

关键词: 四吡啶基卟啉衍生物, 嵌入反应动力学, 铜(Ⅱ)卟啉生成反应

Abstract: Kinetics of the coordination reaction of tetrakis(N-carbomethoxymethyl-3-pyridyl) porphyrin(abbr,H₂T_β-N-ACMSPyP) and tetrakis(N-methylcarbonitrile-3-pyridyl) porphyrin(abbr.H₂T_β-N-ECNSPyP)with Cu(Ⅱ) ion has been studied in latic acid buffer solution in the range of pH 3-5 and an ionic strength of 0.5 mol/L(KCI)at 35.0±0.1℃.The reaction is catalyzed by lactic ion.The effect of concentration of the catalyst and metal ion, and pHvalue of solution was discussed.The observed rate constants of the reaction were obtained as k_obs=k{(1.0+b₁[L]+b₂[L]²)/(1.0+K₃,4[H⁺]²)}[Cu²⁺];k=5.39 mol^-1·L·s^-1,b₁=3.73 ×10² mol^-2·L²·s^-1,b₂=4.76×10⁴ mol^-3·L³·s^-1 for H₂T_β-N-ECNSPyP; k=1.24 mol^-1·L·s^-1,b₁=4.00×10² mol^-2·L²·s^-1,b₂=2.75×10⁵ mol^-3·L³·s^-1 for H₂T_β-N-ECNPyP.The mechanism of the reaction was proposed.The deformation of the ring of porphyrins is the general condition in the reaction.

Key words: Tetra(pyridyl)porphyrin derivative, Kinetics of incorporating reaction, Formation reaction of copper(Ⅱ)porphyrin

TrendMD:

潘志权, 任建国, 秦子斌. 金属离子与卟啉的嵌入反应动力学研究(Ⅳ)──乳酸缓冲体系中四吡啶基卟啉衍生物与铜(Ⅱ)的配位反应. 高等学校化学学报, 1994, 15(4): 565.

PAN Zhi-Quan, REN Jian-Guo, QIN Zi-Bin. Studies on Kinetics of Incorporation of Metal Ion Porpyrin(Ⅳ)──Coordination Reaction of TPyP Derivatives with Cu²⁺ in Lactic Acid Buffer System. Chem. J. Chinese Universities, 1994, 15(4): 565.