| 氯合间取代四苯基卟啉铁与咪唑类配体轴向配位反应的研究 |
| STUDY ON THE AXIAL COORDINATION OF META-SUBSTITUTED TETRAPHENYLPORPHYRINATOIRON(Ⅲ) CHLORIDE WITH IMIDAZOLATES |
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| 摘要: 用紫外可见光谱测量了在丙酮溶剂中氯合间取代四苯基卟啉铁［Fe(m-X)TPPCl, X=-CH3, -Cl］与咪唑(Im), 氯甲基咪唑(N-MeIm), 克霉唑(GMZ)轴配反应平衡常数，并利用温度系数法测定了反应体系的热力学函数ΔrHm和ΔrSm。用停流分光光度法测定了Fe(m-CH3)T |
| 关键词: 氯合间取代四苯基卟啉铁 咪唑 平衡常数 反应机理 |
| 基金项目: |
| Abstract: The thermodynamics of axial coordination reaction of FeⅢ(m-X)TPPCl(X=-CH3, -Cl) with various ligands［L=Im(imidazole), N-MeIm(N-methylimidazole), GMZ(clotrimazole)］ at different temperatures in acetone have been studied. Fe(m-X)TPPCl+nL=Fe(m-X)TPPLn·Cl(1)The equilibrium constant (K) and stoichiometric number (n) of reaction (1) were measured by visible spectral technique. The changes of standard molar enthalpy ΔrH0m and molar entropy ΔrS0m of the reaction(1) were calculated. The steric and electronic effects of the ligands on the reaction were discussed. The kinetic studies for the axial coordination reaction of Fe(m-CH3)TPPCl with Im and N-MeIm in acetone by means of a Union Giken RA-401 stopped-flow spectrophotometer were reported. The mechanisms for both reactions were postulated. The equilibrium constants K of the pre-equilibrium steps and rate constants k of the rate-determininig steps for both of the reactions were evaluated. The ΔrH0m and ΔrS0m of the pre-equilibrium steps and Δ≠Hm, Δ≠Sm of the rate-determining steps for both of the reactions were also calculated. |
| Keywords: meta-substituted tetraphenylporphyrinatoiron(Ⅲ) chloride imidazole equilibrium constant reaction mechanism |
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| 张智慧,邵迎,朱志昂,马刚,阮文娟,周毅,陈荣悌.氯合间取代四苯基卟啉铁与咪唑类配体轴向配位反应的研究[J].无机化学学报,1998,14(2):202-208. |
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