亚碘酰苯氧化Schiff碱配合物反应的取代基效应研究  

Studies on the Substituent Effects on the Oxidation of New Schiff Base Complexes with PhIO

作　　者：陈新斌[1] 杨艳[1] 朱申杰[2] 桂明德[2] 

机构地区：[1]湖南大学化学化工学院,长沙410082 [2]南开大学化学系,天津300071

出　　处：《高等学校化学学报》2001年第4期569-572,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金! (批准号 :2 9472 0 5 5 )资助

摘　　要：用紫外 -可见分光光度分析法测定了 Ph IO氧化系列新型 Schiff碱双核配合物的反应动力学及取代基效应 .结果表明 ,这些配合物与 Ph IO的反应在动力学上为一级反应 ;这些配合物的环外苯基及环上亚苯基上吸电子取代基均能提高抗氧化稳定性 ,而给电子取代基的作用则相反 ;环上亚苯基上的取代基效应比环外苯基上的取代基效应更明显 ;氧化反应速率常数 k与环外苯基上的取代基特性常数σ(σm 或σp)及环上亚苯基上的取代基特性常数 (σm+σp)呈良好的线性关系 :-lgk =0 .52 1 5σ+1 .3 2 6;-lgk =0 .82 71 [(σm+σp) /2 ]+1 .50The kinetic properties and the substituent effects of the oxidations of new Schiff base complexes Mn 2L{L=bis[ N,N  alkylene 2,2 (arylmethylene)bis(3,4 dimethylpyrrole 5 aldimino)]} with PhIO were studied by UV Vis. The results showed that the oxidations are the first order for the complexes. We also found that being contrary to the electron donating groups, the electron withdrowing groups on the phenyl groups or/ and the phenylene groups of the complexes could increase their stabilities; with respect to the antioxidation against PhIO, the substituent effects on the phenylene groups of the complexes are greater than those on the phenyl groups; there are the linear relationships between the reaction kinetic constant k and the substituent constant σ : -lg k =0.521 5 σ + 1.326 for the complexes with substituents on the phenyl groups and -lg k = 0.827 1[( σ m+ σ p)/2] +1.506 for the complexes with substituents on the phenylene groups.

关 键 词：氧化反应 取代基效应 亚碘酰苯氧化西佛碱 锰 双核配合物 双金属单加氧酶 模拟酶 

分 类 号：O614.711[理学—无机化学] Q554[理学—化学]