Synthesis, structure and isomerization of A2Si=SiB 2-type tetrakis(trialkylsilyl)disilenes

Takeaki Iwamoto, Junichiro Okita, Chizuko Kabuto, Mitsuo Kira

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)

Abstract

Two novel A2Si=SiB2-type tetrakis(trialkylsilyl) disilenes: 3(A= t-BuMe2Si, B = i-Pr2MeSi) and 4 (A= t-BuMe2Si, B= i -Pr3Si) were synthesized in good yields. X-ray structural analysis revealed that both 3 and 4 have a twisted Si=Si double bond with a planar arrangement around each of the unsaturated silicon atoms. The twist angle around the Si=Si double bond is remarkably dependent on the substituents and amounts to 27.95(3)° for highly congested disilene 4. Disilene 3 underwent gradually a formal dyotropic rearrangement of trialkylsilyl substituents to give an equilibrium mixture of 3 and (E)- and (Z)-isomers of the corresponding ABSi=SiAB-type disilenes (2E and 2Z ). The activation energy for the isomerization of 3 to 2Z and/or 2E was found to be much smaller than that for the corresponding isomerization of a tetraaryldisilene system.

Original languageEnglish
Pages (from-to)105-111
Number of pages7
JournalJournal of Organometallic Chemistry
Volume686
Issue number1-2
DOIs
Publication statusPublished - 2003 Dec 1

Keywords

  • Dyotropic rearrangement
  • SiNMR
  • Silicon
  • Tetrasilyldisilenes
  • X-ray structural analysis

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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