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

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.