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Materials 2010, 3(2), 1125-1137; doi:10.3390/ma3021125

Chemoselectivity in the Dehydrocoupling Synthesis of Higher Molecular Weight Polysilanes

Institut für Anorganische Chemie, Technische Universität Graz, Stremayrgasse 16, A-8010 Graz, Austria
* Author to whom correspondence should be addressed.
Received: 19 January 2010 / Revised: 29 January 2010 / Accepted: 9 February 2010 / Published: 10 February 2010
(This article belongs to the Special Issue Organometallic Compounds)
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The Cp2ZrCl2/2 BuLi catalyzed co-polymerization of H2MeSiSiMeH2 and PhSiH3 was compared to the homo-polymerization of H2MeSiSiPhH2. In contrast to the co-polymerization, which gave molecular weights comparable to homo-polymerization of phenylsilane, the reaction of 1-methyl-2-phenyldisilane yielded a partially cross-linked high molecular weight polymer with very broad molecular weight distribution. A higher reactivity of phenyl-substituted silicon atoms compared to methyl-substituted ones was detected. Stoichiometric reactions of some disilanes with the slow dehydropolymerization catalyst CpCp*Hf(Cl)Si(SiMe3)3 gave metal disilanyl intermediates with selectivities that reflect the observed polymerization behavior.
Keywords: polysilane; catalysis; group 4 metallocene; dehydrocoupling polymerization polysilane; catalysis; group 4 metallocene; dehydrocoupling polymerization
This is an open access article distributed under the Creative Commons Attribution License (CC BY) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Lunzer, F.; Marschner, C. Chemoselectivity in the Dehydrocoupling Synthesis of Higher Molecular Weight Polysilanes. Materials 2010, 3, 1125-1137.

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