Bicyclic and Polycyclic Systems with a Ring Junction Phosphorus Atom

Tebby, John C.

doi:10.1016/b978-008043952-5/50016-4

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“…Bicyclo[1.1.0]butanes with main-group hetero-elements in the ring have also received considerable attention [ 18 ]. However, little is known about the phosphorus-containing analogues [ 19 – 22 ]. In our ongoing research on small strained organophosphorus ring systems, we became interested in the yet unknown 2-phospha-4-silabicyclo[1.1.0]butanes, whose occurrence we reported as a reactive intermediate recently [ 23 , 24 ].…”

Section: Introductionmentioning

confidence: 99%

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

2006

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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.

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