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类硅烯[CH(R)N]_2SiLiF(R=H和t-Bu)的构型及异构化反应

Theoretical study on the structures and isomerization of Silylenoid (RNCH=CHNR) SiLiF (R=H and t-Bu)
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摘要 用密度泛函理论(DFT)在B3LYP/6-31G(d)计算水平上首次研究了N-杂环类硅烯[CH(R)N]_2SiLiF(R=H和t-Bu)的构型及异构化反应。计算得到了[CH(H)N]_2SiLiF的五个平衡构型和[CH(t-Bu)N]_2SiLiF的四个平衡构型。两种类硅烯的各构型中,包含四元环结构的p-络合物构型都是最稳定的,是实验上可能存在的构型。三元环构型、σ-络合物构型和"经典"四面体构型都是不稳定的。t-Bu基团增强了σ-络合物构型的稳定性,但减小了类硅烯的复合能,从而进一步证明了t-Bu取代的硅烯的稳定性。 The structures and isomerization of N-heterocyclic silylenoid (R=H and t-Bu) were studied by density functional theory (DFT) at B3LYP/6-31G(d) level for the first time. For both two silylenoids, the p-complex structure with a four-membered ring is the most stable form and would be the experimentally detectable one. The three-membered ring structure, σ-complex, and the"classical"tetrahedron structures are active intermediates when silylene (RNCH=CHNR)Si approach to LiF molecule. The stability, reactivity, existence and tert-butyl substituent effects of various equilibrium structures were discussed.
出处 《中国科技论文在线》 CAS 2008年第6期452-458,共7页
基金 扬州大学博士启动基金 教育部博士点基金(20040422010) 杭州师范大学有机硅化学及材料技术教育部重点实验室开放课题科学基金(YJG200701)
关键词 物理化学 类硅烯 DFT 构型异构化 physical chemistry silylenoid DFT isomerization
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