A retro-Diels Alder route to tetramethyldisilene Me2Si= SiMe2 revisited: Flow pyrolysis of 1,1,2,2-Tetramethyl-1,2-disilacyclohex-4-ene

Dong Zhou, Mrinmoy Nag, Amber L. Russel, David Read, Henry W. Rohrs, Michael L. Gross, Peter P. Gaspar

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Reinvestigation of the flow pyrolysis of 1,1,2,2-tetramethyl-1,2-disilacyclohex-4-ene did not identify conditions under which the retro-Diels Alder reaction was the exclusive process. Extrusion of Me2Si=SiMe2was confirmed, but dimerization of directly extruded Me2Si: contributes significantly to its formation. Rearrangement of 1,1,2,2-tetramethyl-1,2-disilacyclohex-4-ene to 1,1,3,3-tetramethyl-1,3-disilacyclohex-4-ene is a major process under a variety of conditions. Computational studies reduced the number of viable pathways. Both experimental and computational results point to stepwise extrusion of Me2Si=SiMe2 via a diradical intermediate and to linkage by one or more common intermediates of the extrusion pathway and the pathway leading to rearranged disilacyclohexene. Such a mechanism receives support from the formation of 1,2- and 1,3-disilacyclohex-4-enes, that is both the Diels-Alder product and the rearrangement product, in the addition of Me2 Si=SiMe2 to butadiene.

Original languageEnglish
Pages (from-to)117-122
Number of pages6
JournalSilicon Chemistry
Volume3
Issue number3-4
DOIs
StatePublished - Jan 2007

Keywords

  • Chemistry
  • Computational
  • Dimethylsilylene
  • Disila-olefin Diels Alder reaction
  • Pyrolysis
  • Reaction mechanism
  • Tetramethyldisilene

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