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The Cp 2 ZrCl 2 /2 BuLi catalyzed co-polymerization of H 2 MeSiSiMeH 2  and PhSiH 3  was compared to the homo-polymerization of H 2 MeSiSiPhH 2 . 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(SiMe 3 ) 3  gave metal disilanyl intermediates with selectivities that reflect the observed polymerization behavior.

Chemoselectivity in the Dehydrocoupling Synthesis of Higher Molecular Weight Polysilanes