Publikation: ansa-metallocene derivatives XXXII. Zirconocene complexes with a spirosilane bridge : syntheses, crystal structures and properties as olefin polymerization catalysts
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Chiral ansa-zirconocene complexes with a trimethylene link between the Si bridge atom and an α-position of each C5 ring ligand were prepared; two representatives, with i-propyl and t-butyl groups as β-substituents, were structurally characterized. The properties of these complexes with respect to MAO-activated propene polymerization were studied in comparison with those of their Me2Si-bridged analogs. The t-butyl-substituted spirosilane complex gives a polymer with relatively high content of 3,1-insertions. These increased regioirregularities appear to be associated with decreased coordination gap aperture and increased lateral extension angles of the spirosilane-bridged zirconocene complexes; this notion is supported by a molecular-mechanics analysis of alternative olefin-insertion transition states.
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MANSEL, Stefan, Ursula RIEF, Marc-Heinrich PROSENC, Robin KIRSTEN, Hans-Herbert BRINTZINGER, 1996. ansa-metallocene derivatives XXXII. Zirconocene complexes with a spirosilane bridge : syntheses, crystal structures and properties as olefin polymerization catalysts. In: Journal of Organometallic Chemistry. 1996, 512(1-2), pp. 225-236. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(95)06073-6BibTex
@article{Mansel1996ansam-23909,
year={1996},
doi={10.1016/0022-328X(95)06073-6},
title={ansa-metallocene derivatives XXXII. Zirconocene complexes with a spirosilane bridge : syntheses, crystal structures and properties as olefin polymerization catalysts},
number={1-2},
volume={512},
issn={0022-328X},
journal={Journal of Organometallic Chemistry},
pages={225--236},
author={Mansel, Stefan and Rief, Ursula and Prosenc, Marc-Heinrich and Kirsten, Robin and Brintzinger, Hans-Herbert}
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<dcterms:abstract xml:lang="eng">Chiral ansa-zirconocene complexes with a trimethylene link between the Si bridge atom and an α-position of each C<sub>5</sub> ring ligand were prepared; two representatives, with i-propyl and t-butyl groups as β-substituents, were structurally characterized. The properties of these complexes with respect to MAO-activated propene polymerization were studied in comparison with those of their Me<sub>2</sub>Si-bridged analogs. The t-butyl-substituted spirosilane complex gives a polymer with relatively high content of 3,1-insertions. These increased regioirregularities appear to be associated with decreased coordination gap aperture and increased lateral extension angles of the spirosilane-bridged zirconocene complexes; this notion is supported by a molecular-mechanics analysis of alternative olefin-insertion transition states.</dcterms:abstract>
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