Solution Structure and Reactivity with Metallocenes of AlMe 2 F: Mimicking Cation–Anion Interactions in Metallocenium–Methylalumoxane Inner‐Sphere Ion Pairs

• Published in: Angewandte Chemie Vol. 129; no. 45; pp. 14415 - 14419
• Main Authors: Oliva, Leone, Oliva, Patrizia, Galdi, Nunzia, Pellecchia, Claudio, Sian, Leonardo, Macchioni, Alceo, Zuccaccia, Cristiano
• Format: Journal Article
• Language: English
• Published: 06-11-2017
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201707194

Abstract
The solution structure of AlMe
2
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, AlMe
2
F gives rise to a complex equilibrium of oligomeric species, including a heterocubane [(Me
2
Al)
4
F
4
] tetramer, resembling the behavior of MAO. This complex mixture reacts with (ETH)ZrMe
2
(ETH=
rac
‐[ethylenebis(4,5,6,7‐tetrahydro‐1‐indenyl)]) to afford [(ETH)ZrMe
δ+
(μ‐F)(AlMe
2
F)
n
AlMe
3
δ−
] inner‐sphere ion pairs through successive insertions/deinsertions of AlMe
2
F units into the Zr⋅⋅⋅(μ‐F) bond.