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合成了六个新的廿员大环双核铜(Ⅱ)配合物作为Cu,Zn-SOD模拟物,其配体是用2,6-二甲酰基吡啶与1,3-丙二胺缩合而成,以SCN~-,Cl~-,Br~-,I~-,N_3~-,OH~-桥联。用多种物理方法进行表征,并用核黄素光照法研究与O_2~-反应的动力学,结果表明反应速率常数大约在10~7mol~(-1)·dm~3·s~(-1),其中以SCN~-为桥的配合物速率常数最高,而含N_3~-桥的最低。ESR谱研究结果表明前者与O_2~-为可逆的催化反应。后者为不可逆的氧化还原反应,这种情况与我们曾研究过的二乙酰基吡啶缩丙二胺合铜配合物一致。N_3~-桥对配合物的阻化作用与N_3~-对SOD的阻化作用类似。
Six new 20-membered macrocyclic binuclear copper (Ⅱ) complexes were synthesized as Cu and Zn-SOD mimics. Their ligands were synthesized by the condensation of 2,6-diformylpyridine and 1,3-propanediamine , With SCN ~ -, Cl ~ -, Br ~ -, I ~ -, N_3 ~ -, OH ~ - bridged. The kinetics of the reaction with O_2 ~ - was studied by a variety of physical methods. The results showed that the reaction rate constant was about 10 ~ 7mol ~ (-1) · dm ~ 3 · s ~ (-1) , Of which SCN ~ - as the bridge the highest rate constant, while containing N_3 ~ - bridge the lowest. ESR spectra showed that the former was reversibly catalyzed by O_2 ~ -. The latter is an irreversible redox reaction, which is in agreement with the diacetylpyridine-4,4’-dipyridine copper complex we have studied. The resistance of N_3 ~ - bridge to the complex was similar to that of N_3 ~ - to SOD.