含冠醚席夫碱钴配合物的双氧亲和力及催化氧化活性

Dioxygen affinities and catalytic oxidation activities of cobalt complexes with Schiff bases containing crown ether.

作者信息

Sun Bin, Chen Junru, Hu Jiayuan, Li Xianjun

机构信息

Department of Chemistry, Sichuan University, No 29, Wangjiang Road, Chengdu, Sichuan Province 610064, PR China.

出版信息

J Inorg Biochem. 2006 Aug;100(8):1308-13. doi: 10.1016/j.jinorgbio.2006.03.004. Epub 2006 Mar 29.

DOI:10.1016/j.jinorgbio.2006.03.004

PMID:16690130

Abstract

The stoichiometry of dioxygen uptake of Co complexes with 4',5'-bis-(5-chloro-2-hydroxyphenylmethylideneimino)benzo-12-crown-4 (1a), 4',5'-bis(2-hydroxyphenylmethylideneimino)benzo-12-crown-4 (1b), 4',5'-bis-(5-methoxy-2-hydroxyphenylmethylideneimino)benzo-12-crown-4 (1c), 4',5'-bis-(5-chloro-2-hydroxyphenylmethylideneimino)benzo-15-crown-5 (2a), 4',5'-bis(2-hydroxyphenylmethylideneimino)benzo-15-crown-5 (2b), 4',5'-bis(5-methoxy-2-hydroxyphenylmethylideneimino)benzo-15-crown-5 (2c) were measured in pyridine solution. The equilibrium constants and thermodynamic parameters (DeltaH0, DeltaS0) of these complexes were calculated. At the same time, their catalytic activities in cyclohexene oxidation to 2-cyclohexen-1-one were examined. The influence of the crown ether ring on the dioxygen affinity of Co complexes at different temperature and the catalytic activities were discussed in comparison with uncrowned analogous complexes.

摘要

在吡啶溶液中测定了钴配合物与4',5'-双-(5-氯-2-羟基苯基亚甲基亚氨基)苯并-12-冠-4（1a）、4',5'-双(2-羟基苯基亚甲基亚氨基)苯并-12-冠-4（1b）、4',5'-双-(5-甲氧基-2-羟基苯基亚甲基亚氨基)苯并-12-冠-4（1c）、4',5'-双-(5-氯-2-羟基苯基亚甲基亚氨基)苯并-15-冠-5（2a）、4',5'-双(2-羟基苯基亚甲基亚氨基)苯并-15-冠-5（2b）、4',5'-双(5-甲氧基-2-羟基苯基亚甲基亚氨基)苯并-15-冠-5（2c）的二氧摄取化学计量。计算了这些配合物的平衡常数和热力学参数（ΔH0、ΔS0）。同时，考察了它们在环己烯氧化为2-环己烯-1-酮中的催化活性。与无冠类似配合物相比，讨论了冠醚环在不同温度下对钴配合物二氧亲和力和催化活性的影响。