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The dehydropolymerisation of phenylsilane is investigated using group 4 metallocene amide complexes as catalysts. The dinuclear zirconocene amide complex Cp 2 Zr(NMe 2 )(μ-Me 3 SiC 3 SiMe 3 )Zr(NMe 2 )Cp 2 (2) (Cp = η 5 -cyclopentadienyl) shows high activity in dehydrocoupling reactions, producing polyphenylsilanes with molecular weights ranging from 200 to 3000 g mol -1 and linear-to-cyclic product ratios of up to 80 : 20. Likewise, different ratios of oligomers and polymers with different tacticities could be described. Ansa -zirconocene amide complexes possessing the ebthi (ebthi = 1,2-ethylene-1,1'-bis(η 5 -tetrahydroindenyl)) ligand systems were prepared and evaluated for catalytic dehydropolymerisation in comparison to the dinuclear catalyst system.

Mono- and dinuclear zirconocene(iv) amide complexes for the catalytic dehydropolymerisation of phenylsilane