A theoretical study of stereochemistry of 1,3-migration in allylsilane and related allylmetallic compounds

Masae Takahashi, Mitsuo Kira

Research output: Contribution to journalArticlepeer-review

28 Citations (Scopus)

Abstract

Ab initio MO calculations for the concerted 1,3-silyl migration in allylsilane at Hartree-Fock and multiconfigurational levels revealed the existence of two transition structures (TS), which lead to retention and inversion of stereochemistry at the silicon. The two structures are pentacoordinate square pyramidal and trigonal bipyramidal around the silicon atom, respectively. The energy barriers estimated at various levels of calculation, including those with electron correlation effects, indicate that the retention transition structure is ca. 9 kcal/mol more stable than the inversion transition structure, in contrast to the experimental results of Kwart et al. Introduction of a π system, such as a vinyl group, at the silicon stabilizes the inversion TS more than the retention TS. Similar transition structures and energetics were obtained for 1,3-migration in allylgermane and allylstannane using effective core potentials for Ge and Sn.

Original languageEnglish
Pages (from-to)1948-1953
Number of pages6
JournalJournal of the American Chemical Society
Volume119
Issue number8
DOIs
Publication statusPublished - 1997 Feb 26
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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