| 硅苯与腈氧化物1,3-偶极环加成反应的理论研究 |
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| 引用本文： | 王岩,张亚,王淑星. 硅苯与腈氧化物1,3-偶极环加成反应的理论研究[J]. 计算机与应用化学, 2012, 0(6): 706-708 |
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| 作者姓名： | 王岩 张亚 王淑星 |
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| 作者单位： | 信阳师范学院化学化工学院 |
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| 基金项目： | 河南省基础与前沿技术研究计划资助项目(092300410207) |
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| 摘 要： | 采用密度泛函理论(DFT)方法在B3LYP/6-311G(d,p)水平研究了硅苯与腈氧化物的1,3-偶极环加成反应的微观机理、势能剖面,考察取代基和四氢呋喃溶剂对反应势能剖面的影响。计算结果表明,所研究反应均以协同但非同步的方式进行,且总是Si-O键先于C-C键形成。硅苯分子中Si原子上的给电子和吸电子取代基均有利于反应的进行,而腈氧化物碳原子上的2,4,6-三甲基苯基取代基在热力学上对反应非常不利。四氢呋喃溶剂对所研究反应的势能剖面影响不大。
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| 关 键 词： | 硅苯 腈氧化物 1,3-偶极环加成反应 反应机理 密度泛函理论 |
Theoretical studies on the 1,3-dipolar cycloaddition reactions between silabenzenes and nitrile oxides |
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| Wang Yan,Zhang Ya and Wang Shuxing. Theoretical studies on the 1,3-dipolar cycloaddition reactions between silabenzenes and nitrile oxides[J]. Computers and Applied Chemistry, 2012, 0(6): 706-708 |
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| Authors: | Wang Yan Zhang Ya Wang Shuxing |
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| Affiliation: | (College of Chemistry and Chemical Engineering,Xinyang Normal University,Xinyang,464000,Henan,China) |
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| Abstract: | The mechanism and potential energy surface of 1,3-dipolar cycloaddition reactions between silabenzenes and nitrile oxides were investigated using density functional theory(DFT) calculations at the B3LYP/6-311G(d,p) level.The influences of substituents and tetrahydrofuran as a solvent on the potential energy surface of reactions were explored.The results show that all of studied reactions proceed via a concerted but asynchronous way and the formation of Si-O bond always keep ahead the formation of C-C bond.Both electron-donating and electron-withdrawing substituents at Si atom of silabenzene molecule favor the 1,3-dipolar cycloaddition reactions,while mesityl substituent at C atom of nitrile oxide have opposite effects thermodyndmically.The influence of tetrahydrofuran solvent on the potential energy surface of the studied reactions is not large. |
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| Keywords: | silabenzene nitrile oxide 1 3-dipolar cycloaddition reaction reaction mechanism density functional theory |
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