2-氨基吡啶金属配合物对羧酸酯水解的催化作用  

Carboxylic Ester Hydrolysis Catalyzed by 2-Aminopyridine Metal Complexes

作　　者：田玉华[1] 黄忠[2] 胡艳[1] 寇兴明[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,四川成都610064 [2]中国工程物理研究院化工材料研究所,四川绵阳621900

出　　处：《催化学报》2005年第3期223-228,共6页

基　　金：国家自然科学基金资助项目 (2 0 173 0 3 8)

摘　　要：合成了 2 氨基吡啶 (2 AP)为配体的Zn(2 AP) 2 (OAc) 2 ,Ni(2 AP) 2 (OAc) 2 和Cu(2 AP) 2 (OAc) 2 三种金属配合物 ,并将其用于催化 2 吡啶甲酸对硝基苯酚酯 (PNPP)和乙酸对硝基苯酚酯 (PNPA)的水解反应 .研究了金属配合物催化PNPP水解的动力学 ,提出了可能的催化机理 .结果表明 ,Zn(2 AP) 2 (OAc) 2 和Ni(2 AP) 2 (OAc) 2 金属配合物对PNPP水解反应有显著的催化作用 ,且Ni(2 AP) 2 (OAc) 2 的催化活性大于Zn(2 AP) 2 (OAc) 2 ,而对PNPA无催化活性 .Cu(2 AP) 2 (OAc) 2 对PNPP和PNPA均无催化活性 .这可能源自底物本身的特性以及配合物结构的差异 .同时 ,实验结果也说明合成的Zn(2 AP) 2 (OAc) 2 和Ni(2 AP) 2 (OAc) 2 是水解金属酶的良好模型 .Zn(2-AP)(2)(OAc)(2), NI(2-AP)(2)(OAc)(2) and Cu(2-AP)(2)(OAc)(2) complexes of 2-aminopyridine (2-AP) were synthesized and their catalytic activity for the hydrolysis of p-nitrophenyl picolinate (PNPP) and P-nitrophenyl acetate (PNPA) was investigated by monitoring the release of P-nitrophenolate. The kinetics for the hydrolysis of PNPP promoted by Zn(2-AP)(2)(OAc)(2) and Ni(2-AP)(2)(OAc)(2) complexes were discussed in detail and the catalytic mechanisms were proposed. The results indicated that Zn(2-AP)(2)(OAc)(2) and Ni(2-AP)(2)(OAc)(2) complexes exhibited very high catalytic activity for the hydrolysis of PNPP and the catalytic activity of Ni(2-AP)(2)(OAc)(2) was higher than Zn(2-AP)2(OAc)2(the apparent second-order rate constants were 4.75 and 7.94 L/(mol center dot s) at PH = 7.0 and 25 degrees C, respectively), but they had no influence on PNPA hydrolysis. The Cu(2-AP)2(OAc)2 complex had no catalytic activity for the hydrolysis of PNPP and PNPA. These results could be attributed to the difference in the substrate nature, complex constituent and complex structure. The results also showed that Zn(2-AP)(2)(OAc)(2) and Ni(2-AP)(2)(OAc)(2) are good models of hydrolytic metalloenzymes.

关 键 词：2-氨基吡啶 锌配合物 镍配合物 铜配合物 羧酸酯 模拟酶 水解 催化动力学 

分 类 号：O643.3[理学—物理化学]