A Study of Thermodynamic in Axial Coordination Reaction of Unsymmetrical Derivatives of Tetraphenylporphyrinatpcobalt(Ⅱ)

Abstract

Abstract: 5-(4-Acetamidophenyl)-10,15, 20-tris (4-methylphenyl) porphyrinatocobalt (Ⅱ)was synthesized. By means of spectrophotometer technique, the equilibrium constants of theaxial coordination reaction were measured between this system and a series of imedazole lig-ands (2-Melm, N-Melm, EMIm, GMZ) which possess different steric hindrances. Theresults show that the size and the position of the substituting group on a ligand influence thestability of the axial coordinative product, and the equilibrium constants appear in the orderK_GMz>K_N-Mclm ＞K_2-Mclm＞K_2-Mclm＞K_EMlm Alinear relationship was observed between △Hand T△Sinboth the symmetrical and unsymmetrical systems. The favorable enthalpy changecompensates the unfavorable entropy change and the compensatory enthalpy- entropy relationshipcontributes to the stability of complexes.

Key words: 5-(4-Acetamidophenyl)-10,15,20-tris(4-methylphenyl)porphyrinatocobalt(Ⅱ), Axial coordination reaction, Equilibrium constants, Steric hindrance, Enthalpy-entropycompensation

CLC Number:

O614.81

TrendMD:

SHAO Ying, ZHU Zhi-Aug, RUAN Wen-Juan, YANG Shao-Ying, TIAN Jian-Hua, MA Gang, ZHANG Zhi-Hui, CHEN Rong-Ti. A Study of Thermodynamic in Axial Coordination Reaction of Unsymmetrical Derivatives of Tetraphenylporphyrinatpcobalt(Ⅱ)[J]. Chem. J. Chinese Universities, 1997, 18(10): 1571.

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A Study of Thermodynamic in Axial Coordination Reaction of Unsymmetrical Derivatives of Tetraphenylporphyrinatpcobalt(Ⅱ)

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