| 氯化原卟啉Ⅸ二甲酯合钴(Ⅲ)的合成及其与咪唑反应动力学的研究 |
| SYNTHESIS OF Co(Ⅲ) PP ⅨDMECI AND KINETIC STUDY OF THE REACTION OF Co(Ⅲ)PPⅨDMECI WITH IMIDAZOLES |
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| 摘要: 从原卟啉Ⅸ(PPⅨ)出发合成氯化原卟啉Ⅸ二甲酯合钴(Ⅲ).分别用元素分析、UV光谱和IR光谱表征。298K时,测定氯化原卟啉Ⅸ二甲酯合钴(Ⅲ)与咪唑反应在丙酮或二氯甲烷溶剂中的表观速率常数kobs,结果表明反应的决速步是单分子咪唑中间体Co(Ⅲ)PPⅨDME(RIm)Cl中氯的离解。总反应速率方程对咪唑是一级反应；氯离解的速率常数k1依赖于溶剂与氯形成氢键的能力,即“远位咪唑氢键效应”;当咪唑中出现2-甲基、2-苯基时,由于取代基与卟 |
| 关键词: 氯化原卟啉Ⅸ二甲酯合钴 咪唑 合成 功力学研究 |
| 基金项目: |
| Abstract: Protoporphyrin Ⅸ dimethyl ester complex of cobalt(Co(Ⅲ)PPⅨDMECl) was synthesized from protoporphyrin Ⅸ(PPⅨ) and characterized by elemental analysis, UV spectrum, IR spectrum and melting point respectively. The observed rate constants(kobs) of the reactions of Co(Ⅲ←)PPⅨ DMECl with imidazoles (RIm) have been investigated in acetone and dichloromethane solvents at 298. 15K. Experiments show that the rate-determining step is chloride ionization from the mono(imidazole) intermediate. The rate law for the overall reaction is the first order in imidazole. The chloride ionization rate constant(k1) strongly depends on the avility of solvent to form hydrogen-bonding, i. c. “distal-imidazole hydrogen bond effect”.When a 2-methyl or 2-phenyl substituent is present the steric strain with porphyrin ligand increases the rate of the trans cholride ionization, i. e.“proximal-strain effect”. |
| Keywords: Co(Ⅲ)PPⅨDMECl imidazole synthesis kinetic study |
| 投稿时间：1993-02-23 |
| 摘要点击次数: 978 |
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| 边平凤,阎卫东,刘湘兰.氯化原卟啉Ⅸ二甲酯合钴(Ⅲ)的合成及其与咪唑反应动力学的研究[J].无机化学学报,1994,10(2):130-135. |
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