类硅烯H2SiLiF 和 CH3XHn-1 (X=F, Cl, Br, O, N; n=1, 1, 1, 2, 3)取代和插入反应的理论研究
首发时间:2008-01-02
摘要:本文用密度泛函的方法,研究了类硅烯H2SiLiF 和 CH3XHn-1 (X=F, Cl, Br, O, N; n=1, 1, 1, 2, 3) 取代反应和插入反应。发现取代反应有两条反应路径,两条路径的反应势垒以CH3NH2 > CH3OH > CH3F > CH3Cl > CH3Br 顺序变化;两条路径得到相同的最终产物H2SiFCH3 和 LiX;在溶剂中,取代反应的势垒随溶剂极性的增大而变大,取代反应势垒的变化趋势与在气相中相同。类硅烯H2SiLiF插入C-X的反应最终可得到H2SiCH3X和LiF。插入反应的势垒以C-Br < C-F < C-Cl < C-O < C-N递增。取代反应比相应的插入反应的势垒低,类硅烯H2SiLiF 和 CH3XHn-1 (X=F, Cl, Br, O, N; n=1, 1, 1, 2, 3)的的反应得到产物中以取代反应的产物为主。
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Theoretical Study on the Substitution and Insertion Reactions of Silylenoid H2SiLiF and CH3XHn-1 (X=F, Cl, Br, O, N; n=1, 1, 1, 2, 3)
Abstract:The substitution and insertion reactions of silylenoid H2SiLiF and CH3XHn-1 (X=F, Cl, Br, O, N; n=1, 1, 1, 2, 3) have been studied by using density functional theory at the B3LYP/6-311+G (d, p) level. There are two paths for the substitution reactions, and the activation barriers decrease in the order ofCH3NH2 > CH3OH > CH3F > CH3Cl > CH3Br in both paths. H2SiFCH3 and LiX are final products of substitution reactions. Calculations about solvent effects on the substitution reactions show that the reaction barriers increase with the the solvent polarity. H2SiCH3X and LiF are the final insertion products of the insertion reactions of silylenoid H2SiLiF into the C-X, and the barriers increase in the order of C-Br < C-F < C-Cl < C-O < C-N. Comparisons between the substitution and insertion reactions indicate substitution reactions prevail over the corresponding insertion reactions.
Keywords: Silylenoid Insertion reactions Substitution reactions DFT
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No.1764218218211992****
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类硅烯H2SiLiF 和 CH3XHn-1 (X=F, Cl, Br, O, N; n=1, 1, 1, 2, 3)取代和插入反应的理论研究
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