Crystal structures and stereospecific propylene polymerizations with chiral hafnium metallocene catalysts

Ligand effects on stereoregulation with homogeneous catalysts have been stimulated considerable interest in Ziegler-Natta propylene polymerizations with metallocene catalysts. The major limitations to development in this area have been that the titanium catalysts are unstable at conventional polymerization temperatures, and that the zirconium analogues only produce low molecular weight oligomers in significant quantities. In this contribution, the authors describe the structures and the polymerization behavior of both rac-ethylenebis(indenyl)hafnium(IV) dichloride (rac-Et(Ind)/sub 2/HfCl/sub 2/) and rac-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV) dichloride (rac-Et-(IndH/sub 4/)/sub 2/HfCl/sub 2/). The results are compared to those with Ti and Zr analogues. The new Hf catalysts are the first metallocenes to provide high yields of high molecular weight isotactic polypropylene.