Abstract
The indene ligands {1‐C~9~H~7~R} [R = C~2~H~4~(C~4~H~7~O~2~) (1), C~2~H~4~(C~3~H~5~O~2~) (2), CH~2~(C~5~H~9~O) (3)] were prepared by alkylation of indene and used to prepare the SiMe~2~‐bridged indenylcyclopentadiene ligands {Me~2~Si(3‐C~9~H~6~R)(C~5~Me~4~H)}[R = C~2~H~4~(C~4~H~7~O~2~) (4), CH~2~(C~5~H~9~O) (5)]. Bis(indenyl)‐and ansa‐indenylcyclopentadienyl zirconocenes [Zr{1‐η^5^‐C~9~H~6~R}~2~Cl~2~] {R = C~2~H~4~(C~4~H~7~O~2~) (6), C~2~H~4~(C~3~H~5~O~2~) (7), CH~2~(C~5~H~9~O) (8)} and [Zr{Me~2~Si(3‐η^5^‐C~9~H~5~R)(η^5^‐C~5~Me~4~)}Cl~2~] {R = C~2~H~4~(C~4~H~7~O~2~) (9), CH~2~(C~5~H~9~O) (10)} were prepared by the reaction of ZrCl~4~ with the appropriate mono‐ or dilithium salts of 1–5. The molecular structure of [Zr{Me~2~Si(3‐η^5^‐C~9~H~5~C~2~H~4~(C~4~H~7~O~2~))(η^5^‐C~5~Me~4~)}Cl~2~] (9) was determined by single‐crystal X‐ray diffraction studies. Indenylzirconium complexes 6–10 were immobilized on thf‐modified MgCl~2~, and these supported systems were used to polymerize ethylene in the presence of methylaluminoxane. The catalytic activity of these complexes in both homogeneous and supported polymerization reactions is discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)