| 氧/硫杂卟啉内氢迁移反应的理论研究 |
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| 引用本文： | 廖玉婷,饶火瑜,曾宏俊,朱霞萍.氧/硫杂卟啉内氢迁移反应的理论研究[J].化学学报,2006,64(21):2138-2144. |
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| 作者姓名： | 廖玉婷 饶火瑜 曾宏俊 朱霞萍 |
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| 作者单位： | (东华理工学院应用化学系 抚州 344000) |
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| 基金项目： | 东华理工学院硕博科研启动基金(No.DHS0429)资助项目. |
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| 摘 要： | 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.
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| 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 |
| 收稿时间： | 2005-12-8 |
| 修稿时间： | 2005年12月8日 |
Theoretical Study on Transfer Reaction of Inner Hydrogen Atoms in Oxa- and Thia-Porphyrins |
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| LIAO,Yu-Ting,RAO,Huo-Yu,ZENG,Hong-Jun,ZHU,Xia-Ping.Theoretical Study on Transfer Reaction of Inner Hydrogen Atoms in Oxa- and Thia-Porphyrins[J].Acta Chimica Sinica,2006,64(21):2138-2144. |
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| Authors: | LIAO Yu-Ting RAO Huo-Yu ZENG Hong-Jun ZHU Xia-Ping |
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| Institution: | (Department of Applied Chemistry, East China Institute of Technology, Fuzhou 344000) |
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| Abstract: | 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 is due to the existence of intra-molecular hydrogen bonds. |
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| Keywords: | inner hydrogen atom transfer (NH tautomerization) oxa- and thia-porphyrin transition state structural change |
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