Enantio- and stereoselective cyclopolymerization of hexa-1,5-diene was achieved by enantiomerically pure dichloro zirconium(IV) pre-catalysts 2 possessing chiral [OSSO]-type bis(phenolate) ligands (-)-1 and (+)-1 in combination with dried methylaluminoxane (dMAO) as an activator. The corresponding activities were recorded with quite high values up to 1,960 g mmol(2) h , which are extremely larger than those of the related complexes. The microstructure analysis for the PMCPs furnished by pre-catalysts (Λ,S,S)-2 and (Δ,R,R)-2 showed good isotacticity factors (α = 75-78%) and relatively high proportions of trans-cyclopentane rings (σ = 14-21%). These enantiomeric PMCPs exhibited large specific optical rotations ([α] = +28 to +32° from (Λ,S,S)-2, -26 to -34° from (Δ,R,R)-2).

Abstract:[OSSO]-type dibenzyl zirconium(IV) complexes 9 and 10 possessing aryl substituents ortho to the phenoxide moieties (ortho substituents, phenyl and 2,6-dimethylphenyl (Dmp)) were synthesized and characterized. Upon activation with dMAO (dried methylaluminoxane), complex 9 was found to promote highly isospecific styrene polymerizations ([mm] = 97.5%-99%) with high molecular weights M w up to 181,000 g¨mmol´1. When the Dmp-substituted pre-catalyst 10/dMAO system was used, the highest activity, over 7700 g¨mmol(10)´1¨h´1, was recorded involving the formation of precisely isospecific polystyrenes of [mm] more than 99%.

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