Novel indenylzirconium complexes as supported catalysts in the polymerization of ethylene

Article abstract of DOI:10.1002/ejic.200500165

A series of substituted indene {C₉H₇R-3 [R = CH ₂CH₂CH₂OSiMe₃ (1), CH ₂CH₂CH₂OCH₂C₆H ₅ (2), CH₂CH₂CH₂OSiMe₂tBu (3)]}, and ansa-indene compounds {Me₂Si(C₉H ₆R-3)₂-1 [R = CH₂CH₂CH ₂OSiMe₃ (4)], Me₂Si(C₉H ₆R-3)-1(C₅HMe₄) [R = CH₂CH ₂CH₂OSiMe₃ (5), CH₂CH ₂CH₂OCH₂C₆H₅ (6), CH ₂CH=CH₂ (7), CH₂CH₂CH ₂OSiMe₂tBu (8)]} have been prepared. The lithium derivatives of 1-8 were employed in the synthesis of the indenylzirconium complexes [Zr(η⁵-C₉H₆R-1) ₂Cl₂] [R = CH₂CH₂CH ₂OSiMe₃ (17), CH₂CH₂CH ₂OCH₂C₆H₅ (18), CH ₂CH₂CH₂OSiMe₂tBu (19)], rac-[Zr{Me₂Si(η⁵-C₉H₅R-3) ₂-1}Cl₂] [R = CH₂CH₂CH ₂OSiMe₃ (20)], [Zr{Me₂Si(η⁵- C₉H₅R-3)-1(η⁵-C₅Me ₄)}Cl₂] [R = CH₂CH₂CH ₂OSiMe₃ (21), CH₂CH₂CH ₂OCH₂C₆H₅ (22), CH ₂CH=CH₂ (23), CH₂CH₂CH ₂OSiMe₂tBu (24)] and [Zr(Me₂Si{η ⁵-C₉H₅(CH₂CH₂CH ₂O)-3}-1{η⁵-C₅Me₄})Cl] (21a). The alkyl complexes [Zr(Me₂Si{η⁵-C₉H ₅(CH₂CH₂CH₂O)-3}- 1{η⁵-C₅Me₄})Me] (25) and [Zr{Me ₂Si(η⁵-C₉H₅R-3)- 1(η⁵-C₅Me₄)}Me₂] [R = CH ₂CH₂CH₂OSiMe₂tBu (26)] have been synthesized by the reaction of the corresponding ansa-zir-conocene derivative with the alkyl Grignard reagent. The molecular structure of [(Zr{C ₉H₆(CH₂CH₂CH₂O)-1}Cl ₂)2(Zr-O)] (17a), a subproduct in the formation of 17 has been determined by single-crystal X-ray diffraction studies. The indenylzirconium complexes 17-24 have been immobilized on partially dehydroxylated SiO ₂, and these supported systems used to polymerize ethylene in the presence of methylaluminoxane. The catalytic activity of these compounds in both homogeneous and heterogeneous polymerization is reported. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.