Skip to main content
SpringerLink
Log in

Oligomer and Polymer Formation in Hexamethylcyclotrisiloxane (D3) – Hydrosilane Systems Under Catalysis by tris(pentafluorophenyl)borane

  • Published:
Journal of Inorganic and Organometallic Polymers and Materials Aims and scope Submit manuscript

Summary

Reactions of hexamethylcyclotrisiloxane, D3, with 1,1,3,3-tetramethyldisiloxane, HMMH, 1,1,1,3,3-pentamethyldisiloxane, HMM, phenyldimethylsilane and phenylmethylsilane catalyzed by tris(pentafluorophenyl)borane were studied. These reactions lead to ring opening of D3 by the SiH reactant producing open chain oligomers with hydrosilane functionality at one or both chain ends. The reactivity of the hydrosilanes toward D3 decreases in the series: PhMeSiH2 > HMMH > PhMe2SiH > HMM. Competitive self-oligomerization of HMMH and HMM also occurs. Primary products of these processes are able to enter into reactions with the SiH and D3 reactants; some also undergo cyclization. Thus, consecutive and competitive processes lead to a series of various oligohomologues. Gas chromatography in conjunction with chemical ionization mass spectroscopy permitted identification of structure and determination of the basic directions of these oligomerization processes. Polysiloxanes of higher molecular weight may be also formed in some of these systems. The reactions, which occur in the systems studied, are rationalized on the basis of the mechanism involving the hydride transfer from silicon to trivalent boron. This includes the transient formation of tertiary trisilyloxonium borate which decomposes by the hydride transfer to one of the silicon atoms of the trisilyloxonium center.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.
Fig. 8.
Fig. 9.
Fig. 10.
Fig. 11.
Fig. 12.

Similar content being viewed by others

References

  1. You-Xian Chen E., Marks T. J.(2000) Chem. Rev. 100:1391

    Article  CAS  Google Scholar 

  2. Coates G. W., Hustad P. D., and Reinartz S.(2002) Angew. Chem. Int. Ed. 41:2236

    Article  CAS  Google Scholar 

  3. Yang Y. G., Choi D. S., and Han S.(2004) J. Polym. Sci., Part A, Polym. Chem. 42:1164

    Article  CAS  Google Scholar 

  4. Ban H. T., Kase T., Kawabe M. et al.(2006) Macromolecules 39:171

    Article  CAS  Google Scholar 

  5. Piers W.E (2005) Adv. Organomet. Chem. 52:1

    Article  CAS  Google Scholar 

  6. G. Erker, J. Chem. Soc. Delton Trans., 1883 (2005)

  7. Hassfeld J., Christmann M., and Kalesse M. (2001) Org. Lett. 3:3561

    Article  CAS  Google Scholar 

  8. Chandrasekhar S., Reddy C. R., and Chandrasekhar G. (2004) Tetrahedron Lett. 45:6481

    Article  CAS  Google Scholar 

  9. Marshall A. J., and Gill K.(2001) J. Organomet. Chem. 624:294

    Article  CAS  Google Scholar 

  10. K. Ishihara, and H. Yamamoto Eur. J. Org. Chem. 527 (1999)

  11. Blackwell J. M., Foster K. L., Beck V. H., and Piers W.E.(1999) J. Org. Chem. 64:4887

    Article  CAS  Google Scholar 

  12. Blackwell J. M., Sonmor E. R., Scoccitti T., and Piers W. E.(2000) Org. Lett. 2:3921

    Article  CAS  Google Scholar 

  13. Gevorgian V., Liu J. -X., Rubin M., Benson V, and Yamamoto Y.(1999) Tetrahedron Lett. 40:8919

    Article  Google Scholar 

  14. Gevorgian V., Rubin M., Benson S., Liu J. -X., and Yamamoto Y.(2000) J. Org. Chem. 65:6179

    Article  CAS  Google Scholar 

  15. Rubinsztajn S. and Cella J.(2005) Macromolecules 38:1061

    Article  CAS  Google Scholar 

  16. Zhou D.Q., and Kawakami Y. (2006) Macromolecules 38:6902

    Article  CAS  Google Scholar 

  17. Chojnowski J., Rubinsztajn S., Cella J., Fortuniak W., Cypryk M., Kurjata J., and Kaźmierski K.(2005) Organometallics 24:6077

    Article  CAS  Google Scholar 

  18. Chojnowski J., Fortuniak W., Kurjata J., Rubinsztajn S., and Cella J.(2006) Macromolecules 39:3802

    Article  CAS  Google Scholar 

  19. G. Belorgey, and G. Sauvet, in Silicon Containing Polymers, R. G. Jones, W. Ando, and J. Chojnowski, eds. (Kluwer Academic Publishers, Dordrecht, 2000), Chap. 2. pp 43–78.

Download references

Acknowledgments

The financial support from General Electric Company is gratefully acknowledged.

Author information

Authors and Affiliations

  1. Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363, Łódź, Poland

    Julian Chojnowski, Witold Fortuniak & Jan Kurjata

  2. General Electric Company, Global Research Center, 1 Research Circle, Niskayuna, Schenectady, NY, 12309, USA

    Slawomir Rubinsztajn

Authors
  1. Julian Chojnowski
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Slawomir Rubinsztajn
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Witold Fortuniak
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jan Kurjata
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Julian Chojnowski.

Additional information

Footnote: This paper is dedicated to Professor Ian Manners in recognition of his significant contributions to the field of organometallic polymers.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chojnowski, J., Rubinsztajn, S., Fortuniak, W. et al. Oligomer and Polymer Formation in Hexamethylcyclotrisiloxane (D3) – Hydrosilane Systems Under Catalysis by tris(pentafluorophenyl)borane. J Inorg Organomet Polym 17, 173–187 (2007). https://doi.org/10.1007/s10904-006-9083-2

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10904-006-9083-2

Keywords

Search

Navigation