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用分光光度法研究了咪唑或吡啶类配体与5-[邻-(4-(1-咪唑基)丁氧基)苯基]-10,15,20-三苯基卟唑合铁(Ⅲ)氯化物[[Fe~Ⅲ(ImTPP)]Cl]和5-[对-(4-(3-吡啶氧基)丁氧基)苯基]-10,15,20-三苯基卟啉合铁(Ⅲ)氯化物[[Fe~Ⅲ(PyTPP)]Cl]两种尾式铁(Ⅲ)卟啉的轴向加合作用,测定了平衡常数、热力学参数及含氮配体的加合分子数.结果表明,[Fe~Ⅲ(PyTPP)Cl与[Fe~Ⅲ(TPP)]Cl相类似,均与咪唑、吡啶类配体生成1:2低自旋六配位加合物.含氮配体与[Fe~Ⅲ(ImTPP)]Cl的轴向加合反应平衡常数比与[Fe~Ⅲ(TPP)]Cl相应的平衡常数大10～10~3倍,这是因为含氮配体与[Fe~Ⅲ(ImTPP)]Cl的轴向配位诱导了尾端咪唑基与配合物中的Fe~Ⅲ离子的轴向配位,这种配位模式增强了含氮配体与Fe~Ⅲ离子的键合;尾端咪唑基与配合物中的Fe~Ⅲ离子配位的模式得到了UV—vis、~1H NMR及EPR实验数据的进一步证实.
The interaction between imidazole or pyridine ligands and iron (Ⅲ) of 5- [o - (4- (1-imidazolyl) butoxy) phenyl] -10,15,20-triphenylpredrazole was studied spectrophotometrically ) Chloride [[Fe ~ III (ImTPP]] Cl] and 5- [p- (4- (3-pyridyloxy) butoxy) phenyl] -10,15,20-triphenylporphyrin Axial Addition of Two Iron (Ⅲ) Porphyrins with Iron [Ⅲ] Chloride [[Fe Ⅲ (PyTPP]] Cl] The equilibrium constants, thermodynamic parameters and adducts of nitrogenous ligands The results show that [Fe ~ (III) (PyTPP) Cl and [Fe ~ III (TPP)] Cl are similar to imidazole and pyridine ligands, respectively, The equilibrium constant ratio of ligand and [Fe ~ III (ImTPP)] Cl is 10 ~ 10 ~ 3 times larger than the equilibrium constant of [Fe ~ III (TPP)] Cl because the nitrogen- Axial coordination with [Fe ~ III (ImTPP)] Cl induces the axial coordination between the tail imidazole groups and Fe ~ III ions in the complex. This coordination mode enhances the coordination of the nitrogen- The binding of the tail imidazole groups to the Fe ~ III ions in the complex was further confirmed by the UV-vis, ~ 1H NMR and EPR experimental data.