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

J. Chris Slootweg, Andreas W. Ehlers, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)531-536
Number of pages6
JournalJournal of Molecular Modeling
Issue number5
Publication statusPublished - Jul 2006
Externally publishedYes


  • Ab initio theory
  • Heterobicyclobutanes
  • Valence isomerization

ASJC Scopus subject areas

  • Catalysis
  • Computer Science Applications
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Computational Theory and Mathematics
  • Inorganic Chemistry


Dive into the research topics of 'Valence isomerization of 2-phospha-4-silabicyclo[1.1.0]butane: A high-level ab initio study'. Together they form a unique fingerprint.

Cite this