去质子化咔咯内氢迁移反应的理论研究  

Theoretical Study on the Inner Hydrogen Atom Transfer Reactions of Deprotonated Corrole

作　　者：廖玉婷 饶火瑜[1] 胡宝群[2] LIAO Yu-ting;RAO Huo-yu;HU Bao-qun(School of Chemistry, Biological and Materials Science, East China University of Technology, Nanchang 330013 ,China;School of Earth Science, East China University of Technology,Nanchang 330013 ,China)

机构地区：[1]东华理工大学化学生物与材料科学学院,江西南昌330013 [2]东华理工大学地球科学学院,江西南昌330013

出　　处：《东华理工大学学报（自然科学版）》2019年第2期181-186,共6页Journal of East China University of Technology(Natural Science)

基　　金：国家自然科学基金资助项目(41472069)

摘　　要：采用B3LYP/6-31G^**方法在Gaussian09程序下,对去质子化咔咯(CH2-)体系进行结构优化和振动分析。结果显示,CH2-的四种不同构型稳定性差异是由内氢原子间距决定的,内氢原子间距大,相对能量低,稳定性高。优化不同构型间相互转化的内氢迁移(IHAT)反应的过渡态,并进行相关的比较计算,各过渡态的能量高低也与内氢原子间距密切相关。CH2-的各构型能量差异大于PH2,同样是从能量最低到能量最高的稳定构型的内氢迁移反应,CH2-的正逆反应速率的差异明显大于PH2。The structures and energies of reactant,product,transition states of the inner transfer reactions( IHAT) of hydrogen atoms in deprotonated corrole( CH2-) are studied. The B3LYP/6-31 G^** method is carried out using Gaussian 09 software. The relative stability of isomers and transition states depends on the distances of inner hydrogen atoms. The distance is longer,the relative energy is lower and relative stability is better. The calculated results show that the difference between of positive and inverse reaction speeds of trans→cis reactions of CH2- are higher than that of porphine( PH2).

关 键 词：咔咯 内氢原子间距 构型的相对稳定性 内氢迁移反应 

分 类 号：O641[理学—物理化学]