Acta Chimica Sinica ›› 2008, Vol. 66 ›› Issue (5): 520-524. Previous Articles     Next Articles

Original Articles

质子化双氧/硫杂卟啉内氢原子迁移反应的理论研究

廖玉婷*,王海江,饶火瑜,周思   

  1. (东华理工大学应用化学系 抚州 344000)
  • 收稿日期:2007-08-07 修回日期:2007-10-28 出版日期:2008-03-14 发布日期:2008-03-14
  • 通讯作者: 廖玉婷

Theoretical Study on the Inner Hydrogen Atom Transfer Reactions of Protonated Di-oxa- or Thia-porphyrin

LIAO Yu-Ting*, WANG Hai-Jiang ,RAO Huo-Yu ,ZHOU Si   

  1. (Department of Applied Chemistry, East China Institute of Technology, Fuzhou 344000)
  • Received:2007-08-07 Revised:2007-10-28 Online:2008-03-14 Published:2008-03-14
  • Contact: LIAO Yu-Ting

On the basis of the stable structures of reactants and products, transfer reactions of inner hydrogen atoms in protonated di-oxa- or thia-porphyrin were studied. The transition states were found and optimized, and the differences between rates of inner hydrogen atom transfer (IHAT) reactions were presented. The calculated results show that the main foctors to affect the relative stability of conformations of the studied protonated molecular systems are aromaticity, the steric hindrance and the electrostatic interaction. The rate differences of IHAT reactions in these protonated double-substitution systems are remarkable. The IHAT reaction rate differences of inner ring substitution mainly resulted from electronic effects rather than conformational changes. In addition, the di-substitutional effects on the IHAT reaction rates are greatly larger than the mono-substitutional effects.

Key words: porphyrin, transition state, structural change, inner hydrogen atom transfer