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Valence isomerization of 2-phospha-4-silabicyclo[1.1.0]butane: a high-level ab initio study

The rearrangements for 2-phospha-4-silabicyclo[1.1.0]butane, analogous to the valence isomerization of the hydrocarbons bicyclobutane, 1,3-butadiene, and cyclobutene, were studied at the (U)QCISD(T)/6-311+G**//(U)QCISD/6-31G* level of theory. The monocyclic 1,2-dihydro-1,2-phosphasiletes are shown t...

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Detalles Bibliográficos
Autores principales: Slootweg, J. Chris, Ehlers, Andreas W., Lammertsma, Koop
Formato: Texto
Lenguaje:English
Publicado: Springer-Verlag 2006
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2441497/
https://www.ncbi.nlm.nih.gov/pubmed/16642334
http://dx.doi.org/10.1007/s00894-005-0041-7
Descripción
Sumario:The rearrangements for 2-phospha-4-silabicyclo[1.1.0]butane, analogous to the valence isomerization of the hydrocarbons bicyclobutane, 1,3-butadiene, and cyclobutene, were studied at the (U)QCISD(T)/6-311+G**//(U)QCISD/6-31G* level of theory. The monocyclic 1,2-dihydro-1,2-phosphasiletes are shown to be the thermodynamically preferred product, in contrast to the isomerization of the hydrocarbons, which favors the 1,3-butadiene structure. Furthermore, an unprecedented direct isomerization pathway to the 1,2-dihydro-1,2-phosphasiletes was identified. This pathway is competitive with the isomerization via the open-chain butadienes and becomes favorable when electron-donating substituents are present on silicon. [Figure: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: Supplementary material is available for this article at http://dx.doi.org/10.1007/s00894-005-0041-7 and is accessible for authorized users.