Computational study of 2-vinylsilirane to silacyclopent-3-ene rearrangement

[1,3]-Sigmatropic rearrangement of 2-vinylsilirane (2-vinylsilacyclopropane) to silacyclopent-3-ene has been studied for the first time with quantum chemical methods. The PBE/TZ2P and B3LYP/6-31G(d) levels of theory have been used to explore the potential energy surface of the title reaction. The en...

Full description

Saved in:
Bibliographic Details
Published in:Journal of molecular structure. Theochem 2010-02, Vol.942 (1), p.60-65
Main Authors: Rynin, S.S., Kulikov, P.V., Faustov, V.I., Boganov, S.E., Egorov, M.P., Nefedov, O.M.
Format: Article
Language:English
Subjects:
(2 + 1) cycloaddition
[1,3]-Sigmatropic rearrangement
G3(MP2)//B3LYP
PBE density functional
Silirane
Silylene
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:[1,3]-Sigmatropic rearrangement of 2-vinylsilirane (2-vinylsilacyclopropane) to silacyclopent-3-ene has been studied for the first time with quantum chemical methods. The PBE/TZ2P and B3LYP/6-31G(d) levels of theory have been used to explore the potential energy surface of the title reaction. The energies of the stationary points have also been evaluated with the G3(MP2)//B3LYP method. Several transition states corresponding to suprafacial and antarafacial pathways of the rearrangement have been found. The lowest energy pathway is a symmetry-allowed suprafacial sigmatropic shift with G3(MP2)//B3LYP activation energy of 97 kJ/mol.
ISSN:0166-1280
1872-7999
DOI:10.1016/j.theochem.2009.11.035