ANSA-METALLOCENE DERIVATIVES .27. CHIRAL ZIRCONOCENE COMPLEXES WITH 2 DIMETHYLSILYLENE BRIDGES

Doubly bridged zirconocene derivatives with C2 symmetrically disposed substituents, ((CH3)2Si)2(3,4-dimethyl-1,2-cyclopentadienediyl)2ZrCl2 (4A) and ((CH3)2Si)2(4,5,6,7-tetrahydro-1,2-indenediyl)2ZrCl2 (4B) were synthesized by reactions of the corresponding ligand dilithium salts with ZrCl4 in toluene; the racemic isomers were obtained by fractionated crystallization of the diastereomeric product mixtures. X-ray diffraction studies give space group P1BAR with a = 9.596 (5) angstrom b = 13.160(7) angstrom, c = 16.645 (9) angstrom, alpha = 96.60 (4)-degrees, beta = 90.33 (4)-degrees, gamma = 98.66 (4)-degrees, and Z = 4 (two crystallographically independent molecules) for 4A and space group P2(1)/n with a 9.994 (4) angstrom, b = 15.04O(6) angstrom, c = 15.078(8) angstrom, beta = 95.09(4)-degrees, and Z = 4 for 4B. Both complexes show the expected C2-axial symmetry. In combination with methylalumoxane, 4A and 4B are slowly converted to catalysts for the polymerization of propene, which yield polymers with low and medium isotacticities, respectively. Control experiments indicate that conversion of these complexes to active catalysts involves degradation of their strained ligand frameworks; intact 4A and 4B do not appear to give rise to catalytic activity.