1. Computational study of 2-vinylsilirane to silacyclopent-3-ene rearrangement
- Author
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Rynin, S.S., Kulikov, P.V., Faustov, V.I., Boganov, S.E., Egorov, M.P., and Nefedov, O.M.
- Subjects
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REARRANGEMENTS (Chemistry) , *CYCLOPROPANE , *SILICON compounds , *QUANTUM chemistry , *POTENTIAL energy surfaces , *ACTIVATION (Chemistry) , *FORCE & energy , *DENSITY functionals - Abstract
Abstract: [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 97kJ/mol. [Copyright &y& Elsevier]
- Published
- 2010
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