Probing the interactions between all components of the catalytic pool for homogeneous olefin polymerisation by diffusion NMR spectroscopy

Rocchigiani, Luca ORCID: https://orcid.org/0000-0002-2679-8407, Busico, Vincenzo, Pastore, Antonello and Macchioni, Alceo (2013) Probing the interactions between all components of the catalytic pool for homogeneous olefin polymerisation by diffusion NMR spectroscopy. Dalton Transactions, 42 (25). pp. 9104-9111. ISSN 1477-9226

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Abstract

Diffusion NMR spectroscopy was applied to investigate all individual components and combinations thereof for the Cp2ZrMe2/MAO (DMAO)/TBP (MAO = methylaluminoxane, DMAO = AlMe3 depleted MAO, TBP = 2,6-di-tert-butylphenol) ternary system, selected as a prototypical catalytic pool for homogeneous olefin polymerisation. Both MAO and DMAO were found to self-aggregate in C6D6 with the latter having a higher propensity. TBP reacts with DMAO affording MeAl(2,6-di-tert-butylphenoxide)2 and causing a structural modification of DMAO, whose aggregates become much larger. The actual dimensions and self-aggregation tendency of (D)MAO, which depend on Al concentration and the possible presence of TBP, turned out to carry over to [Cp2Zr(μ-Me)2AlMe2]MeMAO (1) OSIP (outer sphere ion pair) and [Cp2Zr+Me⋯MeMAO−] (2) ISIP (inner sphere ion pair) that form upon activation of Cp2ZrMe2. Once the intrinsic self-aggregation tendency of MAO has been subtracted, OSIP 1 and ISIP 2 behave exactly as analogous ion pairs with borate ions: ISIP 2 does not self-aggregate, whereas OSIP 1 exhibits the same self-aggregation trends of zirconocene OSIPs with borate counterions.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry
Related URLs:	http://www.scopus.com/inward/record.url?...
Depositing User:	LivePure Connector
Date Deposited:	20 Jun 2019 00:03
Last Modified:	22 Oct 2022 04:52
URI:	https://ueaeprints.uea.ac.uk/id/eprint/71497
DOI:	10.1039/c3dt00041a

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