Computational study of reaction pathways in the course of interaction of deactivated silylenes with buta-1,3-diene |
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Authors: | SS Rynin MP Egorov OM Nefedov |
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Institution: | N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospekt 47, 119991 Moscow, Russian Federation |
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Abstract: | The PESs of systems including deactivated silylenes (SiHHal, SiHal2, Hal = F, Cl, and 2-silaimidazol-2-ylidene, SiN2H2C2H2) and buta-1,3-diene have been studied using G3(MP2)//B3LYP method. Two major reaction channels, (2 + 1) and (4 + 1) cycloaddition reactions, leading to 2-vinylsiliranes and silacyclopent-3-enes, respectively, as well as 1,3]-sigmatropic rearrangements between 2-vinylsiliranes and the corresponding silacyclopent-3-enes, have been considered in detail. Reactivity of silylenes toward buta-1,3-diene decreases in the following series: SiHHal > SiHal2 > SiN2H2C2H2, which is reflected in increase of the reaction barriers for both cycloaddition reactions and in decrease of exothermicity of the formation of the corresponding products. The (4 + 1) cycloaddition is preferable for SiHal2 and SiN2H2C2H2 and can compete with (2 + 1) cycloaddition for SiHHal. 1,3]-Sigmatropic rearrangement is important for isomerization of 2-vinylsiliranes to the corresponding silacyclopent-3-enes for all systems studied, except the SiCl2 system. |
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Keywords: | Silylenes Siliranes (2 + 1) Cycloaddition (4 + 1) Cycloaddition [1 3]-Sigmatropic rearrangement G3(MP2)//B3LYP |
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