铁(Ⅲ)卟啉轴向配位反应热力学研究

Studies on the Thermodynamics of Axial Coordination Reaction of Porphinatoiron( Ⅲ )

对金属卟啉与咪唑类物质的轴向配位反应的研究始于对生物化学酶的结构模拟。随着卟啉化学研究的深入和扩展,人们逐渐发现轴向配体的作用不容忽视。对各类卟啉体系,轴向配体的存在与否常会产生很大的影响。因此,研究卟啉化合物的轴向配位反应具有重要意义。

A thermodynamic study is reported for the axial coordination of meso-tetrame-sitylporphinatoiron (Ⅲ) chloride (Fe(Ⅲ)TMPCl) with imidazole (Im), 2-methylimidazole (Melm), clotrimazole (CMZ ) , 2-ethyl-4-methylimidazole (EMIm ) and 4'-imidazol-1-yl-ace-tophenone(ImAPh) in dichloromethaneFe( Ⅲ )TMPC1 + nL [Fe(Ⅲ)TMPLn]+ Cl- (1)The equilibrium constant (β) and stoichiometric number(n) of reaction (1) were measured by spectrophotometer technique. The standard molar enthalpy change (ΔHm) and standard molar entropy changc(ΔSm) of the reaction were calculated. The nuclear magnetic resonance spectra of both before and after the axial coordination reaction of Fe( Ⅲ)TMPC1 were recorded by MSL-400 Bruker superconduction nuclear magnetic resonance spectrometer.