TY - JOUR
T1 - Valence isomerization of 2-phospha-4-silabicyclo[1.1.0]butane: a high-level ab initio study
AU - Slootweg, J.C.
AU - Ehlers, A.W.
AU - Lammertsma, K.
PY - 2006
Y1 - 2006
N2 - 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. © Springer-Verlag 2006.
AB - 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. © Springer-Verlag 2006.
U2 - 10.1007/s00894-005-0041-7
DO - 10.1007/s00894-005-0041-7
M3 - Article
SN - 1610-2940
VL - 12
SP - 531
EP - 536
JO - Journal of Molecular Modeling
JF - Journal of Molecular Modeling
IS - 5
ER -