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化学学报
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化学学报 ›› 1999, Vol. 57 ›› Issue (3): 298-304. 上一篇    下一篇

研究论文

冠醚化单和双Schiff碱的合成及其钴(II)配合物的氧加合性能

李建章;秦圣英;李仲辉;阳华   

  1. 四川大学化学系.成都(610064)
  • 发布日期:1999-03-15

Synthesis of crowned mono- and bis-schiff bases and dioxygen affinities of their cobalt(II) complexes

Li Jianzhang;Qin Shengying;Li Zhonghui;Yang Hua   

  1. Sichuan Univ, Dept Chem.Chengdu(610064)
  • Published:1999-03-15

由苯并-15-冠-5经硝化、还原和缩合反应,制备了4'-(2-羟基苯亚甲基亚氨基)苯并-15-冠-5(L^1H)和4',5'-双(2-羟基苯亚甲基亚氨基)苯并-15-冠-5(L^4H~2)以及它们的取代衍生物L^2H和L^5H~2。在不同温度和不同轴配体存在下,测定了它们的钴(II)配合物的氧合常数和ΔHⅲ,ΔSⅲ,并与未冠醚化的类似物CoL~2^3和CoL^6比较,讨论了配体结构和轴配体碱性对配合物的氧分子加合性能的影响。

关键词: 冠醚, 席夫碱, 钴络合物, 氧合反应, 硝基化, 还原, 缩合

Four crowned mono- and bis-Schiff bases, 4'-(2- hydroxyphenylmethylideneimino) benzo-15-crown-5 (L^1H) and 4', 5'-bis (2-hydroxyphenylmethylideneimino) benzo-15-crown-5 (L^4H~2) as well as their substituted derivatives L^2H, L^5H~2 were prepared from benzo- 15-crown-5 via nitration, reduction, and condensation. Equilibrium constants and thermodynamic constants ΔHⅲ, ΔSⅲ for oxygenation of these crowned cobalt(II) Schiff base compleses were measured. The influence of ligand structure and basicity of axial ligand on the affinities of the complexes for dioxygen was discussed in comparison with uncrowned analoques.

Key words: CROWN ETHER, SCHIFF BASE, COBALT COMPLEX, NITRATION, REDUCTION, CONDENSATION

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