卟啉化合物研究Ⅲ.桥链冠醚卟啉化合物及其钴配合物的合成与轴向配位

卟啉化合物研究Ⅲ.桥链冠醚卟啉化合物及其钴配合物的合成与轴向配位 STUDIES OF PORPHYRIN COMPOUNDS Ⅲ. Synthesis of bridged crowned porphyrins and their cobalt（Ⅱ） complexes 夏淑贞 Xia Shuzheng 1 first-author 姜照慈 Jiang Zhaoci 1 柯汉忠 Huang Suqiu 1 章锦华 1 黄素秋 1 武汉大学化学系 武汉大学化学系 Department of Chemistry, Wuhan University Department of Chemistry, Wuhan University 合成了5,15-二对羟苯基-10,20-二对甲氧苯基卟啉（1）,5,10-二对羟苯基-15,20-二对甲氧苯基卟啉（2）,四个桥链冠醚卟啉（6a,6b,7a,7b）以及6a,7a的钴（Ⅱ）配合物（6a-Co Ⅱ ,7a-Co Ⅱ ）。用分光光度法研究了在二氯甲烷中6a-Co Ⅱ 与咪唑、吡啶、2-甲基吡啶,2,6-二甲基吡啶的配位作用,测定了配位平衡常数,并探讨了光照对6a-Co Ⅱ 与2,6-=甲基吡啶的配位反应的影响。结果表明:6a-Co Ⅱ 与这些有机碱均为1:1作用,它们的平衡常数大小顺序是咪唑 > 吡啶 > 2-甲基吡啶 > 2,6-二甲基吡啶;光照能大大加快6a-Co Ⅱ 与2,6-二甲基吡啶的作用。 5, 15-di-p-hydroxyphenyl-10, 20-di-p-methoxyphenylporphyrin（1）, 5,10-di-p-hydroxypheny1-15, 20-di-p-methoxyphenylporphyrin（2）, four bridged crowned porphyrins （6a, b, 7a, b） and two cobalt（Ⅱ） complexes （6a-Co Ⅱ , 7a-Co Ⅱ ） have been synthesized. Their structure were confirmed. Coordination properties of the 6a-Co Ⅱ with imidazole, pyridine, a-picoline and 2, 6-lutidine were studied and the equilibrium constants for addition of these bases to 6a-Co Ⅱ in dichloromethane have been measured by spectral techniques. In addition, coordination of 6a-Co Ⅱ with 2, 6-lutidine on irradiation were probed. Experiment results demontrate that all these bases react with 6a-Co Ⅱ to form 1:1 adduct in dichloromethane. Irradiation speeds up greatly the addition of 6a-Co Ⅱ with 2, 6-lutidine. 卟啉 冠醚 合成 载氧体 porphyrin crown oxygen carriers synthesis 1991-03-01 2021-04-01 3