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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 3.0).

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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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