SIOC English
化学学报
高级检索

化学学报 ›› 2006, Vol. 64 ›› Issue (21): 2138-2144. 上一篇    下一篇

研究论文

氧/硫杂卟啉内氢迁移反应的理论研究

廖玉婷*, 饶火瑜, 曾宏俊, 朱霞萍   

  1. (东华理工学院应用化学系 抚州 344000)
  • 投稿日期:2005-12-08 修回日期:2006-07-21 发布日期:2006-11-14
  • 通讯作者: 廖玉婷

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

LIAO Yu-Ting*; RAO Huo-Yu; ZENG Hong-Jun; ZHU Xia-Ping   

  1. (Department of Applied Chemistry, East China Institute of Technology, Fuzhou 344000)
  • Received:2005-12-08 Revised:2006-07-21 Published:2006-11-14
  • Contact: LIAO Yu-Ting

PDF

766

被引次数

26 | 1

采用B3LYP/6-31G**方法在Gaussian 03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.

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

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 calculated 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 is due to the existence of intra-molecular hydrogen bonds.

Key words: inner hydrogen atom transfer (NH tautomerization), oxa- and thia-porphyrin, transition state, structural change