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Modification of methylaluminoxane-activated ansa-zirconocene catalysts with triisobutylaluminum-transformations of reactive cations studied by NMR spectroscopy

Modification of methylaluminoxane-activated ansa-zirconocene catalysts with triisobutylaluminum-transformations of reactive cations studied by NMR spectroscopy

Type of Publication: Journal article
URI (citable link): http://nbn-resolving.de/urn:nbn:de:bsz:352-236687
Author: Babushkin, Dmitrii E.; Brintzinger, Hans-Herbert
Year of publication: 2007
Published in: Chemistry - A European Journal ; 13 (2007), 18. - pp. 5294-5299. - ISSN 0947-6539. - eISSN 1521-3765
Pubmed ID: 17385201
DOI (citable link): https://dx.doi.org/10.1002/chem.200601801
Summary:
When triisobutylaluminum (AliBu3) is added to solutions containing methylaluminoxane (MAO) and rac-[Me2Si(ind)2ZrCl2] (ind: indenyl) in C6D6, NMR spectra show that methyl-bridged mixed-alkylaluminum dimers Al(μ-Me)2Me4−xiBux predominate. These dimers react with MAO under partial transfer of isobutyl groups and induce a conversion of the initially prevailing cationic trimethylaluminum adduct rac-[Me2Si(ind)2Zr(μ-Me)2AlMe2+] to rac-[Me2Si(ind)2Zr(μ-Me)2AlMeiBu+] and rac-[Me2Si(ind)2Zr(μ-Me)2AliBu2+]. These species are unstable and release isobutene under formation of zirconocene hydrides.
Subject (DDC): 540 Chemistry
Keywords: Aluminum alkyls, metallocenes, methylaluminoxane, polymerization, structure–activity relationships
Link to License: Terms of use

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BABUSHKIN, Dmitrii E., Hans-Herbert BRINTZINGER, 2007. Modification of methylaluminoxane-activated ansa-zirconocene catalysts with triisobutylaluminum-transformations of reactive cations studied by NMR spectroscopy. In: Chemistry - A European Journal. 13(18), pp. 5294-5299. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.200601801

@article{Babushkin2007Modif-23668, title={Modification of methylaluminoxane-activated ansa-zirconocene catalysts with triisobutylaluminum-transformations of reactive cations studied by NMR spectroscopy}, year={2007}, doi={10.1002/chem.200601801}, number={18}, volume={13}, issn={0947-6539}, journal={Chemistry - A European Journal}, pages={5294--5299}, author={Babushkin, Dmitrii E. and Brintzinger, Hans-Herbert} }

terms-of-use 2007 eng 2013-07-11T08:00:29Z When triisobutylaluminum (AliBu<sub>3</sub>) is added to solutions containing methylaluminoxane (MAO) and rac-[Me<sub>2</sub>Si(ind)<sub>2</sub>ZrCl<sub>2</sub>] (ind: indenyl) in C<sub>6</sub>D<sub>6</sub>, NMR spectra show that methyl-bridged mixed-alkylaluminum dimers Al(μ-Me)<sub>2</sub>Me<sub>4</sub>−xiBux predominate. These dimers react with MAO under partial transfer of isobutyl groups and induce a conversion of the initially prevailing cationic trimethylaluminum adduct rac-[Me<sub>2</sub>Si(ind)<sub>2</sub>Zr(μ-Me)<sub>2</sub>AlMe<sub>2</sub><sup>+</sup>] to rac-[Me<sub>2</sub>Si(ind)<sub>2</sub>Zr(μ-Me)<sub>2</sub>AlMeiBu<sup>+</sup>] and rac-[Me<sub>2</sub>Si(ind)<sub>2</sub>Zr(μ-Me)<sub>2</sub>AliBu<sub>2</sub><sup>+</sup>]. These species are unstable and release isobutene under formation of zirconocene hydrides. Babushkin, Dmitrii E. Brintzinger, Hans-Herbert Babushkin, Dmitrii E. 2013-07-11T08:00:29Z Modification of methylaluminoxane-activated ansa-zirconocene catalysts with triisobutylaluminum-transformations of reactive cations studied by NMR spectroscopy Chemistry : A European Journal ; 13 (2007), 18. - S. 5294-5299 Brintzinger, Hans-Herbert

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