Novel indenylzirconium complexes as supported catalysts in the polymerization of ethylene

A series of substituted indene {C9H7R-3 [R = CH2CH2CH2O-SiMe3 (1), CH2CH2CH2OCH2C6H5 (2), CH2CH2CH2OSiMe2-tBu (3)]}, and ansa-indene compounds {Me2Si(C9H6R-3)(2)-1 [R = CH2CH2CH2OSiMe3 (4)], Me2Si(C9H6R-3)-1(C5HMe4) [R = CH2CH2CH2OSiMe3 (5), CH2CH2CH2OCH2C6H5 (6), CH2CH=CH2 (7), CH(2)CH(2)CH(2)OSiMe(2)tBu (8)]} have been prepared. The lithium derivatives of 1-8 were employed in the synthesis of the indenylzirconium complexes [Zr(eta(5)- C9H6R-1)(2)Cl-2] [R = CH2CH2CH2OSiMe3 (17), CH2CH2CH2OCH2C6H5 (18), CH(2)CH(2)CH(2)OSiMe(2)tBu (19)], rac-[Zr{Me2Si(eta(5) -C9H5R-3)(2)-1)Cl-2] [R = CH2CH2CH2OSiMe3 (20)], [Zr(Me2Si(eta(5)-C9H5R-3)-1 (eta(5)-C5Me4)}Cl-2] [R = CH2CH2CH2OSiMe3 (21), CH2CH2CH2OCH2C6H5 (22), CH2CH=CH2 (23), CH2CH2CH2OSiMe2tBu (24)] and [Zr(Me2Si(eta(5)-C9H5(CH2CH2CH2O)-3}-1[eta(5)-C5Me4})Cl] (21a). The alkyl complexes [Zr(Me2Si{eta(5)-C9H5(CH2CH2CH2O)-3}-1(eta(5) -C5Me4})Me] (25) and [Zr{Me2Si(eta(5)-C9H5R-3)-1(eta(5)-C5Me4)}Me-2] [R = CH(2)CH(2)CH(2)OSiMe(2)tBu (26)] have been synthesized by the reaction of the corresponding ansa-zirconocene derivative with the alkyl Grignard reagent. The molecular structure of [(Zr{C9H6(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 SiO2, 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. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).