Synthesis, Structure, and Catalytic Properties of ansa-zirconocenes, Me2Si(RInd)2ZrCl2 (R = 2-p- or 3-p-toly)

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ansa-Ligands, Me2Si(RInd)2 [R2-p (1) and 3-p-tolyl (2)], have been prepared as a mixture of rac- and meso-isomers in a ratio of 1:1 from the reactions of Me2SiCl2 with cyanocuprates of 1-p-tolylindene and 2-p-tolylindene in diethyl ether, respectively. Pure rac-isomers, 1r and 2r, have been isolated by fractional recrystallization of 1 and 2. Thermal diastereomerization of 1 and 2 between rac- and meso-isomers has been studied by 1H-NMR spectroscopy. These results imply that 1 and 2 undergo the diastereomerization process by migration of silicon moiety and hydrogen atom, respectively. ansa-Zirconocenes, Me2Si(RInd)2ZrCl2 [R2-p (3) and 3-p-tolyl (4)], have been prepared from the reactions of the corresponding dilithiated ligands with ZrCl4 in diethyl ether and hexane at 78°C. The molecular structure of rac-3 has been determined by a single crystal X-ray diffraction study. Propylene polymerization has been studied using rac-3 and meso-4 in the presence of methylaluminoxane (MAO). Catalyst rac-3 produces a highly isotactic polypropylene (PP) at 0°C by the nantiomorphic site control mechanism and meso-4 affords a syndiotactic dominant PP having a rr triad of 49% at 30°C by the chain end control mechanism.
Publisher
Elsevier
Issue Date
1998
Keywords

ansa-Zirconocene; Tolylindene; Diastereomerization; Propylene polymerization; Crystal structure

Citation

Journal of Organometallic Chemistry, Vol.559, pp.149-156

ISSN
0022-328X
URI
http://hdl.handle.net/10203/20142
Appears in Collection
CH-Journal Papers(저널논문)

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