| 双氧/硫杂紫菜嗪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,王海江,邹丽霞,胡宝群.双氧/硫杂紫菜嗪内氢迁移反应的理论研究[J].计算机与应用化学,2011,28(2). |
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| 作者姓名： | 廖玉婷 饶火瑜 王海江 邹丽霞 胡宝群 |
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| 作者单位： | 1. 东华理工大学放射性地质与勘探技术国防重点学科实验室,江西,抚州,344000;东华理工大学刘成东实验室,江西,抚州,344000
2. 东华理工大学应用化学系,江西,抚州,344000 |
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| 基金项目： | 国家自然科学基金(No.40862005); 江西省教育厅科技项目(No.GJJ10506); 东华理工大学校长基金(No.DHXK0820),东华理工大学放射性地质与勘探技术国防重点学科实验室开放基金(No.2010RGET05) |
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| 摘 要： | 本文在确定各反应体系反应物和产物稳定构象的基础上,采用B3LYP/6-31G~(**)方法利用Gaussian 03程序,对质子化的双氧/硫杂紫菜嗪的内氢迁移反应进行了研究,寻找并优化相应的过渡态,比较了其迁移反应速率的差异。计算结果表明,在中心空穴较小的体系中,空间位阻和静电作用对构象稳定性的影响显著增强,并有可能超越共轭效应而成为影响构象的首要因素。另外,在体系的总电子不变的前提下,缩小中心空穴,提高芳香性,有助于电荷的平均分布,可以明显减弱取代基对IHAT反应速率的影响。
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| 关 键 词： | 卟啉 紫菜嗪 过渡态 结构变化 内氢迁移 |
Theoretical study on the inner hydrogen atom transfer reactions of di-oxa-or thia-porphyrin |
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| Liao Yuting,Rao Huoyu,Wang Haijiang,Zou Lixia,Hu Baoqun.Theoretical study on the inner hydrogen atom transfer reactions of di-oxa-or thia-porphyrin[J].Computers and Applied Chemistry,2011,28(2). |
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| Authors: | Liao Yuting Rao Huoyu Wang Haijiang Zou Lixia Hu Baoqun |
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| Affiliation: | Liao Yuting~(1,2*),Rao Huoyu~3,Wang Haijiang~3,Zou Lixia~3 and Hu Baoqun~(1,2) (1.Key Laboratory of Radioactive Geology and Exploration Technology Fundamental Science for National Defense,East China Institute of Technology,Fuzhou,344000,Jiangxi,China) (2.Key Laboratory of Liu Chengdong,China) (3.Department of Applied Chemistry,China) |
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| Abstract: | With the stable conformations of all the reactants and products,the inner transfer reaction of hydrogen atoms in protonated di-oxa- or thia-porphyrin are studied in this worked.The B3LYP/6-31G~(**) method is carried out using Gaussian 03 software.The transition states are found and optimized,and the speeds of different IHAT reactions are compared.The results show that,in the molecule system with smaller central holes,the steric hindrance and the electrostatic interaction have more impact on the relative sta... |
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| Keywords: | porphyrin porphyrazine transition state structural changes inner hydrogen atom transfer(IHAT) |
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