四(邻甲氧基)苯基卟啉钴(Ⅱ)轴向配位反应的热力学研究  

STUDY ON THE THERMODYNAMICS OF AXIAL COORDINATION REACTION OF TETRAPHENYLP- ORPHYRINATOCOBALT WITH IMIDAZOLES

作　　者：胡珍珠[1] 朱志昂[2] 

机构地区：[1]湖北师范学院化学与环境工程系,湖北黄石435002 [2]南开大学化学系,天津300071

出　　处：《南开大学学报（自然科学版）》2003年第4期68-71,共4页Acta Scientiarum Naturalium Universitatis Nankaiensis

基　　金：国家自然科学基金资助项目(20171024)

摘　　要：用分光光度法测量了四(邻甲氧基)苯基卟啉钴(Ⅱ)与咪唑、2-甲基眯唑、吡啶、2-甲基毗啶轴向配位反应的平衡常数,并利用温度系数法求得了反应体系的热力学函数△rHmθ和△rSmθ和△rSmθ结果表明,这些轴配反应的平衡常数呈现K2-MeIt>KIm>K2-MePy>Kpy的趋势,且均为放热、熵减的过程;该反应体系中△rHmθ与△rSmθ间存在线性关系,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。The equilibrium constants on the axial coordinate reaction of α,β,γ,δ-tetra (o-methoxyphenyl) porphyrinatocobalt (Ⅱ) (or : CoTPP) complex with imidazoles, 2-MeIm, pyridine and 2-picoline were determined by spectrometric methods. Experiment results demonstrated that all these nitrogenous ligands reacted with CoTPP to form 1 : 1 adduct in DMF, and the equilibrium constants appeared in the order of K2-MeIm>KIm>K2-MePy>Kpy.The effects of solvent on the reactions were discussed. The changes of standard molar enthalpy △rHmθand the changes of standard molar entropy △rSmθof the reaction were obtained from the plots of lnKθvs 1/T. The favourable enthalpy change compensates the unfavourable entropy change and the compensatory enthalpy-entropy relationship contributes to the stability of complexes.

关 键 词：四(邻甲氧基)苯基卟啉钴(Ⅱ) 轴向配位 热力学 熵焓补偿 

分 类 号：O614.81[理学—无机化学]