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尾式金属卟啉配合物的研究——Ⅳ.含氮配体与尾式铁(Ⅲ)卟啉轴向配位反应热力学及其配位模式 被引量:11

Studies on Tailed Metalloporphyrin Coordination Compounds——Ⅳ. Thermodynamics for the Axial Addition of Nitrogenous Ligands to Tailed Porphyrin Iron (Ⅲ) Complexes and the Novel Coordination Mode
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摘要 用分光光度法研究了咪唑或唑啶类配体与5-[邻-(4-(1-咪唑基)丁氧基)苯基]-10,15,20-三苯基卟啉合铁(Ⅲ)氯化物[[Fe^Ⅲ(ImTPP)]Cl和5-[对-(4-(3-吡啶氧基)丁氧基)丁氧基]-10,15,20-三苯基卟啉合铁(Ⅲ)氯化物[[Fe^Ⅲ(PyTPP)]Cl]两种尾式铁(Ⅲ)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, Coordination properties between two new tailed porphyrin iron (Ⅲ) complexes, 5-[o-(4-(1-imidazolyl)butoxyl)phenyl]-10,15, 20-triphenylporphyrinatoiron (Ⅲ) chloride {[FeⅢ(ImTPP)]Cl} and 5-[p-(4-(3-pyridyloxyl)butoxyl]phenyl-10, 15, 20-triphenylporphyrinatoiron (Ⅲ) chloride {[FeⅢ (PyTPP)]Cl}, with nitrogenous ligands and the equilibrium constants for the addition of these ligands to [FeⅢP]Cl in chloroform were studied by spectral technique. Experimental results demonstrated that [FeⅢ(PyTPP)]Cl, just similar to [FeⅢ(TPP)]C1, form 1:2 adducts with imidazole or pyridines, respectively, but [ FeⅢ(ImTPP)] Cl forms only 1:1 adducts with pyridines and form 1:2 adduct with imidazole. The equilibrium constants for the addition of nitrogenous ligands to [FeⅢ(ImTPP)]Cl are 10- 103 times as big as those for [FeⅢ(TPP)]Cl system. We believe that this result is from the fact that the axial coordination of these ligands to [ FeⅢ(ImTPP)] Cl induces the coordination of terminal imidazole group with ferric iron in [FeⅢ(ImTPP)]Cl and this kind of coordination mode strengthens the bonding between ferric ion in [FeⅢ(ImTPP)]Cl and nitrogen atom in ligand. The novel coordination mode and its structure were identified by the experimental data from UV-vis, 1H NMR and low-temperature EPR.
机构地区 中山大学化学系
出处 《化学学报》 SCIE CAS CSCD 北大核心 1995年第9期861-866,共6页 Acta Chimica Sinica
基金 国家自然科学基金 广东省自然科学基金 兰州大学应用有机化学国家重点实验室 南京大学配位化学国家重点实验室资助
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