二十四元六氮大环双核铜(I)配合物的氧化去甲基作用: 单加氧酶的模拟

以5-溴-2-甲氧基-1, 3-苯二甲醛与二乙烯三胺通过2+2]缩合,合成了一个新的六氮杂二十四元大环配体, 并在Cu(CH3CN)4]ClO4存在下生成Cu(I)大环配合物, 然后在空气(或氧气)中氧化, 得到了新的大环双核Cu(II)配合物, 用多种方法对其进行了表征, 用1H NMR谱等方法鉴定了氧化产物。实验结果表明: 在Cu(I)配合物氧化过程中,能使配体环上的一个甲氧基发生断裂, 形成苯氧桥和水桥联的Cu(II)配合物。在木质素酶等单加氧酶的氧化过程中也伴随着氧化去甲基作用。本文首次用大环配合物对这一过程进行了模拟, 并测定了氧化反应中的吸氧量和吸氧速率常数。

The oxidative demethylation of 24-membered hexa-aza macrocyclic bicopper(I) complex : The mimicking for monooxygenase

By 2+2] Schiff base condensation of 5-bromo-2-methoxylbenzene-1, 3-dicarboxaldehyde with diethylenetriamine, a new hexaaza 24-membered macrocyclic ligand was obtained, which formed a macrocyclic binuclear copper (I) complex in the presence of Cu.(CH3CN)4]ClO4. When the copper(I) complex was oxidized in air or oxygen, a new macrocyclic binuclear copper(II) complex was obtained. The copper(II) complex was characterized by several methods and its oxidized products was characterized by 1H NMR. The results show that during oxidation, a methoxyl group in the ligand ring broke, and the phenoxy- and water-bridged Cu(II) complex formed. In oxidation of monooxygenase such as ligninase, oxidative demethylation also happened. Therefore this work mimicked this process for the first time by using macrocyclic complex. The quantity of absorbed oxygen and the absorption rate of oxygen were determined.