高等学校化学学报

高等学校化学学报 ›› 2000, Vol. 21 ›› Issue (9): 1441.

• 论文 • 上一篇    下一篇

链型氮氧杂醇酚胺多齿配体Cu(Ê)和Zn(Ê)配合物催化NA酯水解研究

解永树1, 郁隽1, 林瑞森2, 刘清亮1   

  1. 1. 中国科学技术大学化学系, 合肥 230026;
    2. 浙江大学化学系, 杭州 310027
  • 收稿日期:1999-09-15 出版日期:2000-09-24 发布日期:2000-09-24
  • 通讯作者: 解永树(1971年出生),男,博士,教授,从事生物无机化学研究.E-mail:yshxie@ustc.edu.cn E-mail:yshxie@ustc.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29773041)资助

4-Nitrophenyl Acetate Hydrolysis Catalyzed by Cu(Ê) and Zn(Ê) Complexes of Linear Oxa-Aza Polydentate Amino Alcoholic Phenol Ligands

XIE Yong-Shu1, YU Jun1, LIN Rui-Sen2, LIU Qing-Liang1   

  1. 1. Department of Chemistry, University of Science and Technology of China, Hefei 230026, China;
    2. Department of Chemistry, Zhejiang University, Hangzhou 310027, China
  • Received:1999-09-15 Online:2000-09-24 Published:2000-09-24

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摘要： 在25±0.1℃,I(KNO3)=0.10mol/L,pH=6.5～9(50mmol/L缓冲溶液)条件下,用分光光度法测定了含醇羟基和酚羟基链型氮氧杂配体N,NØ-二-(2-羟乙基)-乙二胺(L1)和N-(2-羟基苄基)-3-氨基-1-丙醇(HL2)的Cu(Ê)配合物及N-(2-羟乙基)-NØ-(2-羟基苄基)-乙二胺(HL3)和N-(2-羟乙基)-二乙三胺(L4)的Zn(Ê)配合物催化对硝基苯酚乙酸酯(NA)水解动力学,得到了NA酯催化水解二级反应速率常数kC.结果表明,在中性pH值附近生成的配位烷氧负离子Cu(Ê)……-OR和Zn(Ê)……-OR均为很好的亲核试剂.配合物对NA酯水解有亲核试剂进攻和金属离子作为Lewis酸活化底物的双重催化作用,kC值可分别达到6.72×10-2,0.126,4.55×10-2和7.66×10-2mol-1·L·s-1.

关键词: 氮氧杂配体, 催化水解, Cu(Ê, )配合物, Zn(Ê, )配合物, 亲核试剂

Abstract: The kinetics of p-nitrophenyl acetate(NA) hydrolysis catalyzed by Cu(Ê) complexes of ligands N,NØ-bis-(2-hydroxyethyl)-ethylenediamine(L1) and N-(2-hydroxybenzyl)-3-amino-propan-1-ol(HL2) and Zn(Ê) complexes of ligands N-(2-hydroxyethyl)-NØ-(2-hydroxybenzyl)-ethylenediamine(HL3) and 3,6,9-triaza-1-nonanol(L4) was determined spectrophotometrically at (25±0.1) ℃ and I=0.10 mol/L KNO3 in U(CH3CN)=10% at pH 6.5—9.0(50 mmol/Lbuffers), and the second-rate constants kC for the catalysis of NAester hydrolysis were obtained. The experimental results indicate that coordinated alkoxides Cu(Ê)… -ORand Zn(Ê)… -ORyielded at neutral pHare strong nucleophiles, and the complexes have a strong ability to catalyze the hydrolysis of NAester following the double-catalysis mechanism, with kC values of 6.72×10-2, 0.126 , 4.55×10-2 and 7.66×10-2 mol-1·L·s-1.

Key words: Oxa-aza ligands, Catalytic hydrolysis, Cu(Ê, ) complexes, Zn(Ê, ) complexes, Nucleophiles

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