Chapter 14. Silylene and Disilene Reactions with Some 1, 3-Dienes and Diynes

  1. Prof. Norbert Auner2 and
  2. Prof. Johann Weis3
  1. Lars Kirmaier and
  2. Manfred Weidenbruch

Published Online: 28 APR 2008

DOI: 10.1002/9783527619917.ch14

Organosilicon Chemistry IV: From Molecules to Materials

Organosilicon Chemistry IV: From Molecules to Materials

How to Cite

Kirmaier, L. and Weidenbruch, M. (2000) Silylene and Disilene Reactions with Some 1, 3-Dienes and Diynes, in Organosilicon Chemistry IV: From Molecules to Materials (eds N. Auner and J. Weis), Wiley-VCH Verlag GmbH, Weinheim, Germany. doi: 10.1002/9783527619917.ch14

Editor Information

  1. 2

    Inst. für Anorganische Chemie, der Universität Frankfurt, Marie-Curie-Strasse 11, D-60439 Frankfurt am Main, Germany, Phone: 0 69/7 98-29180, -29591, Fax: 069/798-29188

  2. 3

    Wacker-Chemie GmbH, Geschäftsbereich S, Werk Burghausen, Johannes-Hess-Strasse 24, D-84489 Burghausen, Germany

Author Information

  1. Fachbereich Chemie, Universität Oldenburg Carl-von-Ossietzky-Straje 9, D-26111 Oldenburg, Germany Tel.: Int. code + (441)798 3655— Fax: Int. code + (441)798 3352

Publication History

  1. Published Online: 28 APR 2008
  2. Published Print: 17 JAN 2000

ISBN Information

Print ISBN: 9783527298549

Online ISBN: 9783527619917

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Keywords:

  • silylene;
  • disilene;
  • silaheterocycles;
  • 1,3-dienes;
  • diynes

Summary

Di-tert-butylsilylene (2), generated together with tetra-tert-butyldisilene (3) by photolysis of hexa-tert-butylcyclotrisilane (1), reacted with the five-membered heterocyclic compounds 2, 5-dimethyltellurophene and N-methylpyrrole to furnish the corresponding substituted 1, 3-ditellura-2, 4-disiletane (8) and 2-aza-3-silabicyclo[2.2.0]hex-2-ene (9) ring systems. Upon heating, compound 9 rearranged to a 1-aza-2-silacyclohexa-3, 5-diene derivative. Further treatment of 9 with 2 yielded the 1-aza-2, 5-disilacylohepta-3, 6-diene 11. Reaction of the intermediates 2 and 3 with the triple bonds of hexa-2, 4-diyne afforded the rearranged addition products 2-methylene-5-methyl-3, 4, 7, 8-tetrasilabicyclo[4.2.0]oct-1(6)ene (12) and 2-methyl-3-propynylsilirene (13). Renewed treatment of 13 with 2 afforded the 2, 5-disilabicyclo[2.2.0]hexa-1(6), 3-diene ring system (15). A similar reaction of 1 with 1, 4-bis(trimethylsilyl)buta-1, 3-diyne led to an unprecedented insertion of 2 into the C-C single bond of the diyne to provide the bis(alkynyl)silane 16, which was isolated together with the bicyclic compound 17, in which the methyl groups of 15 are replaced by SiMe3 groups.