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  

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

作　　者：焦向东[1] 黄锦汪[1] 计亮年[1] 

机构地区：[1]中山大学化学系,广州510275

出　　处：《化学学报》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

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.

关 键 词：卟啉 轴向配位反应 配合物 铁 

分 类 号：O614.811[理学—无机化学] O641.4[理学—化学]