Synthesis, characterization and compared reactivity of asymmetrical ansa-metallocenes

Rac and meso ansa-zirconocenes [Zr{1-Me2Si(3-R-(η5-C9H5))(3-R′-(η5-C9H5))}Cl2] (R = Et, R′ = H; R = Pr, R′ = H; and R = Et, R′ = Pr) 4–9 have been prepared by the reaction of ZrCl4 with the corresponding dilithiated derivatives from the ligands {1-Me2Si(3-R-(η5-C9H5))(3-R′-(η5-C9H5))} (R = Et, R′ = H 1; R = Pr, R′ = H 2; and R = Et, R′ = Pr 3) in diethyl ether/toluene at −78 °C. The molecular structure of rac [Zr{1-Me2Si(3-Et-(η5-C9H5))(3-Pr-(η5-C9H5))}Cl2] 8 has been determined by single crystal X-ray diffraction studies, which show a pseudotetrahedral environment formed by the two chlorine ligands and two η5-coordinated indenyl ligands. The activity in homogeneous and heterogeneous polymerization is compared and discussed.