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New Synthetic Strategies for Structured Silicones Using B(C6F5)3

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Silicon Polymers

Part of the book series: Advances in Polymer Science ((POLYMER,volume 235))

Abstract

The dehydrocarbonative condensation of alkoxysilanes + hydrosilanes in the presence of the Lewis acid catalyst B(C6F5)3 (R3SiOR′ + HSiR3 ′′ → R3SiOSiR3 ′′ + R′H) – described throughout this review as the Piers-Rubinsztajn reaction – provides a new, mild strategy for the controlled synthesis of silicones. In this review we examine the mechanistic parameters that control the reaction, and outline the types of accessible small molecules, linear, branched, and cross-linked materials (resins and elastomers) that can be prepared using this and related reactions.

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Notes

  1. 1.

    Rubinsztajn, Chojnowski, and I have discussed why, in their hands, metathesis is frequently encountered, while we typically do not observe it. One possible explanation is the order of addition of reagents. Typically, we add catalyst to a mixture of the hydrosilane and alkoxysilane, while Chojnowski and coworkers use one of two alternate strategies (see Sect. 4.1). It is clear, nevertheless, that metathesis does not occur under all reaction conditions.

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Acknowledgements

We gratefully acknowledge the financial support of the Natural Sciences and Engineering Research Council of Canada (NSERC), Silcotech Canada, Siltech Canada, and Centre National de la Recherche Scientifique (CNRS). We also thank Prof. Alan Bassindale (Open University, UK), Prof. Warren Piers (Calgary), and Prof. Martin Oestreich (Münster) for helpful discussions.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada, L8S 4M1

    Michael A. Brook & John B. Grande

  2. Institut Charles Gerhardt UMR5253 CNRS, Equipe «Ingénierie et Architectures Macromoléculaires», Ecole Nationale Supérieure de Chimie de Montpellier, 8 Rue de l’Ecole Normale, Montpellier, Cedex, 34296, France

    François Ganachaud

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  1. Michael A. Brook
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  2. John B. Grande
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  3. François Ganachaud
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Correspondence to Michael A. Brook .

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Editors and Affiliations

  1. Moscow State University, Inst. Synthetic Polymeric Materials, Russian Academy of Sciences, ul. Profsoyuznaya 70, Moskva, 117393, Russian Federation

    Aziz M. Muzafarov

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Brook, M.A., Grande, J.B., Ganachaud, F. (2010). New Synthetic Strategies for Structured Silicones Using B(C6F5)3 . In: Muzafarov, A. (eds) Silicon Polymers. Advances in Polymer Science, vol 235. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2009_47

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