| 二氯硅烯与乙烯和甲醛环加成反应机理的理论研究 |
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| 引用本文： | 卢秀慧,王沂轩,刘成卜.二氯硅烯与乙烯和甲醛环加成反应机理的理论研究[J].高等学校化学学报,1999,20(4):612-615. |
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| 作者姓名： | 卢秀慧 王沂轩 刘成卜 |
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| 作者单位： | 1. 济南大学化学系, 济南 250002;
2. 山东大学化学院, 济南 250100 |
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| 摘 要： | 用RHF/6-31G*解析梯度方法研究了单重态二氯硅烯与乙烯和甲醛环加成反应的机理,并用二级微扰方法对各构型能量进行了相关能校正.结果表明,两反应历程均由两步组成:(1)二氯硅烯与乙烯和甲醛分别生成了中间配合物,是无势垒的放热反应;(2)中间配合物异构化成产物二氯硅杂环丙烷和二氯硅杂环氧甲烷,其势垒经零点能校正分别为97.43和103.29kJ/mol(MP2/6-31G*//6-31G*).
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| 关 键 词： | 二氯硅烯 环加成反应 从头算 过渡态 |
| 收稿时间： | 1998-06-02 |
Theoretical Study on the Cycloaddition Reaction of Dichlorosilylene and Ethylene or/and Formaldehyde |
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| LU Xiu-Hui,WANG Yi-Xuan,LIU Cheng-Bu.Theoretical Study on the Cycloaddition Reaction of Dichlorosilylene and Ethylene or/and Formaldehyde[J].Chemical Research In Chinese Universities,1999,20(4):612-615. |
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| Authors: | LU Xiu-Hui WANG Yi-Xuan LIU Cheng-Bu |
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| Institution: | 1. Department of Chemistry, Jinan University, Jinan, 250002;
2. Institute of Chemistry, Shandong University, Jinan, 250100 |
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| Abstract: | The mechanism of the cycloaddition reaction of singlet dichlorosilylene and ethylene or/and formaldehyde has been studied by RHF/6\|31G\+* gradient method. The electron correlation energies of all the structures are calculated by using second\|order Moller\|Plesset perturbation theory(MP2). The results show that the two reaction proceesses are both two steps: (1) dichlorosilylene and ethylene or/and formaldehyde form an intermediate complex respectively, which is a exothermal reaction with no barrier; (2) two intermediate complexes isomerized to the products respectively, the barriers of the two reactions are 97\^43 and 103\^29 kJ/mol at MP2/6\|31G\+*//6\|31G\+* with zero\|point energies correction level.\= |
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| Keywords: | Dichlorosilylene Cycloaddition reaction \%Ab initio\% calculation Transition state |
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