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Angew Chem Int Ed Engl. 2017 Nov 6;56(45):14227-14231. doi: 10.1002/anie.201707194. Epub 2017 Oct 6.

Solution Structure and Reactivity with Metallocenes of AlMe2 F: Mimicking Cation-Anion Interactions in Metallocenium-Methylalumoxane Inner-Sphere Ion Pairs.

Author information

1
Dipartimento di Chimica e Biologia "Adolfo Zambelli", Università di Salerno, Via Giovanni Paolo II, 132-84084, Fisciano (SA), Italia.
2
Dipartimento di Chimica, Biologia e Biotecnologie, Università degli Studi di Perugia, Via Elce di Sotto, 8-06123, Perugia, Italia.

Abstract

The solution structure of AlMe2 F and its reactivity with a prototypical ansa-metallocene have been investigated by advanced NMR techniques, in an attempt to indirectly shed some light on the structure and working principles of methylalumoxane (MAO) mixtures in olefin polymerization. In solution, AlMe2 F gives rise to a complex equilibrium of oligomeric species, including a heterocubane [(Me2 Al)4 F4 ] tetramer, resembling the behavior of MAO. This complex mixture reacts with (ETH)ZrMe2 (ETH=rac-[ethylenebis(4,5,6,7-tetrahydro-1-indenyl)]) to afford [(ETH)ZrMeδ+ (μ-F)(AlMe2 F)n AlMe3δ- ] inner-sphere ion pairs through successive insertions/deinsertions of AlMe2 F units into the Zr⋅⋅⋅(μ-F) bond.

KEYWORDS:

NMR spectroscopy; aluminum fluoride; ion pairs; methylalumoxane; olefin polymerization

PMID:
28925536
DOI:
10.1002/anie.201707194

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