应用Fukui函数探讨双苯基-取代的自由基闭环反应的区位选择性  

Exploring the regioselectivity of biphenyl-substituted radical ring closure addition by Fukui function

作　　者：杨忠志[1] 徐珍珍[1] 

机构地区：[1]辽宁师范大学化学化工学院,辽宁大连116029

出　　处：《辽宁师范大学学报（自然科学版）》2012年第2期193-196,共4页Journal of Liaoning Normal University:Natural Science Edition

基　　金：国家自然科学基金项目(21133005;20873055;21073080)

摘　　要：应用概念密度泛函理论下的反应性指标Fukui函数,结合局域硬软酸碱(HSAB)原理,解释和预测双苯基-取代的自由基闭环反应的区位选择性,其中活性指标是通过ABEEMσπ模型获得的.通过研究得出,发生反应的反应中心的Fukui函数差的绝对值(Δf)能够预测出,5号碳原子更容易被自由基进攻,这与实验上的区位选择性是一致的.此外,主要产物的Δf值预测出的反应活性序列与实验上的速率常数有很好的关联一致性.In this thesis, the regioselectivities of biphenyl-substituted radical ring closure additions were investigated by the Fukui function combined with the local HSAB principle. And we also used the Fukui function to predict their reactivity sequence, where all the reactivity descriptors were ob- tained by ABEEMerr model. According to the local HSAB principle,the results were obtained through Fukui function that the double-bonded Cs atom was attacked easily by radical atom C1 ,which were in agreement with the experimental regioselectivities. Furthermore, the Fukui function can rationalize the reactivity sequence of intramolecular reactions well. This order is in line with the experimental re- action rate constants.

关 键 词：Fukui函数 局域HSAB原理 ABEEMΣΠ模型 区位选择性 

分 类 号：O641.121[理学—物理化学]