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Hirvi JT, Bochmann M, Severn JR, et al. Formation of octameric methylaluminoxanes by hydrolysis of trimethylaluminum and the mechanisms of catalyst activation in single-site α-olefin polymerization catalysis. Chemphyschem. 2014;15(13):2732-42doi: 10.1002/cphc.201402298.
Hirvi, J. T., Bochmann, M., Severn, J. R., & Linnolahti, M. (2014). Formation of octameric methylaluminoxanes by hydrolysis of trimethylaluminum and the mechanisms of catalyst activation in single-site α-olefin polymerization catalysis. Chemphyschem : a European journal of chemical physics and physical chemistry, 15(13), 2732-42. https://doi.org/10.1002/cphc.201402298
Hirvi, Janne T, et al. "Formation of octameric methylaluminoxanes by hydrolysis of trimethylaluminum and the mechanisms of catalyst activation in single-site α-olefin polymerization catalysis." Chemphyschem : a European journal of chemical physics and physical chemistry vol. 15,13 (2014): 2732-42. doi: https://doi.org/10.1002/cphc.201402298
Hirvi JT, Bochmann M, Severn JR, Linnolahti M. Formation of octameric methylaluminoxanes by hydrolysis of trimethylaluminum and the mechanisms of catalyst activation in single-site α-olefin polymerization catalysis. Chemphyschem. 2014 Sep 15;15(13):2732-42. doi: 10.1002/cphc.201402298. Epub 2014 Jun 16. PMID: 24930450.
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Chemphyschem. 2014 Sep 15;15(13):2732-42. doi: 10.1002/cphc.201402298. Epub 2014 Jun 16.

Formation of octameric methylaluminoxanes by hydrolysis of trimethylaluminum and the mechanisms of catalyst activation in single-site α-olefin polymerization catalysis.

Chemphyschem : a European journal of chemical physics and physical chemistry

Janne T Hirvi, Manfred Bochmann, John R Severn, Mikko Linnolahti

Affiliations

  1. Department of Chemistry, University of Eastern Finland, Joensuu Campus, 80101 Joensuu (Finland).

PMID: 24930450 DOI: 10.1002/cphc.201402298

Abstract

Hydrolysis of trimethylaluminum (TMA) leads to the formation of methylaluminoxanes (MAO) of general formula (MeAlO)n (AlMe3)m. The thermodynamically favored pathway of MAO formation is followed up to n=8, showing the major impact of associated TMA on the structural characteristics of the MAOs. The MAOs bind up to five TMA molecules, thereby inducing transition from cages into rings and sheets. Zirconocene catalyst activation studies using model MAO co-catalysts show the decisive role of the associated TMA in forming the catalytically active sites. Catalyst activation can take place either by Lewis-acidic abstraction of an alkyl or halide ligand from the precatalyst or by reaction of the precatalyst with an MAO-derived AlMe2(+) cation. Thermodynamics suggest that activation through AlMe2(+) transfer is the dominant mechanism because sites that are able to release AlMe2(+) are more abundant than Lewis-acidic sites. The model catalyst system is demonstrated to polymerize ethene.

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Keywords: ab initio calculations; ion pairs; metallocenes; reaction mechanisms; structure elucidation

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