双环八氮杂大环双核铜配合物催化羧酸酯水解研究  

Catalytic Hydrolysis of p-Nitrophenyl Picolinate (PNPP) by a Dinuclear Copper(Ⅱ) Complex of an Octaaza Di-macrocyclic Ligand

作　　者：寇兴明[1] 胡艳[1] 田玉华[1] 孟祥光[1] 胡常伟[1] 曾宪诚[1] 

机构地区：[1]四川大学化学学院四川省绿色化学与技术重点实验室,成都610064

出　　处：《无机化学学报》2005年第1期51-58,共8页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.20173038No.20107004)

摘　　要：合成了一类新的双环二氧大环四胺双核铜配合物,其组成经元素分析、热重/差热分析、摩尔比法及等物质的量连续变化法所确证。在水溶液中,详细研究了其催化2-吡啶甲酸对硝基苯酚酯(PNPP)水解的动力学和机理,并与相应的单核铜配合物进行了对比。结果表明,此双核铜配合物能有效地催化PNPP的水解;两个金属中心之间具有明显的协同作用,较好的模拟了某些天然水解金属酶的“双功能催化机理”。A new dinuclear copper(Ⅱ) complex of an octaaza di-macrocyclic ligand (bisdioxocyclam) has been synthesized and characterized by elementary analysis, TG/DTA, molar ratio and Job method. Its ability to catalyze the hydrolysis of PN PP was studied and the kinetics and mechanism for the hydrolysis of PNPP promote d by the dinuclear copper(Ⅱ) complex of bisdioxocyclam was discussed in detail. For comparision, the catalytic activity of the corresponding mononuclear copper( Ⅱ) complex toward the hydrolysis of PNPP was also investigated. The results ind i cate that the macrocyclic dinuclear copper(Ⅱ) complex of bisdioxocyclam can eff e ctively catalyzed the hydrolysis of PNPP. Apparent cooprativity between two meta l ions of the macrocyclic dinuclear copper(Ⅱ) complex was observed, which is si m ilar to the 'bifunctional mechanism' operated by some natural hydrolytic metallo enzyme.

关 键 词：双核铜配合物 PNPP 连续变化法 摩尔比法 羧酸酯 催化 物质的量 水解 热重 合成 

分 类 号：O614.121[理学—无机化学] O643[理学—化学]