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...
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
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.
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
inner hydrogen atom transfer （NH tautomerization）
oxa- and thia-porphyrin
transition state
structural change
