休克尔分子轨道方法与量子化学计算相结合理解链状共轭体系的H[1,j]σ迁移反应  

Understanding the Regioselectivity of H[1,j]σ Migrations Using HMO Theory and Quantum Chemical Calculations

作　　者：赵容浩 朱荣秀[1] 张冬菊[1] ZHAO Rong-Hao;ZHU Rong-Xiu;ZHANG Dong-Ju(School of Chemistry and Chemical Engineering,Shandong University,Jinan 250100,China)

机构地区：[1]山东大学化学与化工学院,山东济南250100

出　　处：《化学教育（中英文）》2023年第16期121-124,共4页Chinese Journal of Chemical Education

基　　金：国家自然科学基金(22273051);山东省高等教育本科教学改革研究项目(Z2022169);山东大学教育教学改革研究项目(2022Y072)。

摘　　要：σ迁移反应是本科化学类专业基础化学中的重要内容,其反应的区域选择性是教学的重点。以戊二烯衍生物为例,讨论其H[1,j]σ迁移反应及其区域选择性。应用休克尔分子轨道(HMO)理论,导出了最简单4n+1和4n-1型链状共轭体系(即n=1)的π分子轨道能级和波函数;用量子化学方法计算了戊二烯衍生物H[1,3]σ迁移和H[1,5]σ迁移的过渡态结构及其相对能量,验证了戊二烯衍生物在加热条件下将发生H[1,5]σ迁移而不是H[1,3]σ迁移。σ-migration reactions are the important teaching content in basic chemistry courses for undergraduate chemistry majors,and the regioselectivity of the reactions is a key point to teaching and learning.In this paper,the H[1,j]σmigration reactions of a pentadiene derivative and their regioselectivity are discussed.Based on the Hückel molecular orbital method,the energy levels and molecular orbitals ofπelectrons in the simplest 4n+1 and 4n-1 linear conjugated systems are derived,which rationalizes the regioselectivity of the H[1,j]σmigrations of the pentadiene derivative under heating and light conditions.The structures and relative energies of the transition states of 1,3-and 1,5-H migrations of the pentadiene derivative are calculated by performing density functional theory calculations,and the calculated results verify that the pentadiene derivative prefers to perform the 1,5-H migration rather than the 1,3-H migration.

关 键 词：HMO方法 FMO理论 H[1 j]σ迁移 DFT计算 

分 类 号：O641.1[理学—物理化学]