氧/硫杂卟啉内氢迁移反应的理论研究  

Theoretical Study on Transfer Reaction of Inner Hydrogen Atoms in Oxa-and Thia-Porphyrins

作　　者：廖玉婷[1] 饶火瑜[1] 曾宏俊[1] 朱霞萍[1] 

机构地区：[1]东华理工学院应用化学系,抚州344000

出　　处：《化学学报》2006年第21期2138-2144,共7页Acta Chimica Sinica

基　　金：东华理工学院硕博科研启动基金(No.DHS0429)资助项目.

摘　　要：采用B3LYP/6-31G**方法在Gaussian03程序下,对氧杂卟啉(OPH),硫杂卟啉(SPH)的结构和能量进行优化,并寻找与内氢迁移反应相关的过渡态构型.计算结果表明,由于分子内氢键的存在,氧或硫杂化均会使卟吩内氢迁移正负反应速率明显降低.A theoretical study of the mechanism and kinetics of the inner hydrogen atom-transfer process in oxa-porphyrin (OPH) and thia-porphyrin (SPH) was presented. The structures and energies of reactants, products and transition-states in the transfer reaction of inner hydrogen atoms in OPH and SPH were calcu- lated with B3LYP/6-31G** method under certain symmetry restriction. The calculated results show that compared with porphine (PH2), oxa- or thia- can decrease speeds of positive and negative reactions, which...

关 键 词：内氢迁移(NH的互变异构化) 氧/硫杂卟啉 过渡态 结构变化 

分 类 号：O643.12[理学—物理化学]