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Issue 48, 2018
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Modifying methylalumoxane via alkyl exchange

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Abstract

Methylalumoxane (MAO) ionizes highly selectively in the presence of octamethyltrisiloxane (OMTS) to generate [Me2Al·OMTS]+ [(MeAlO)16(Me3Al)6Me]. We can take advantage of this transformation to examine the reactivity of a key component of MAO using electrospray ionization mass spectrometry (ESI-MS), and here we describe the reactivity of this pair of ions with other trialkyl aluminum (R3Al) components. Using continuous injection methods, we found Et3Al to exchange much faster and extensively at room temperature in fluorobenzene (t½ ∼2 s, up to 25 exchanges of Me for Et) than iBu3Al (t½ ∼40 s, up to 11 exchanges) or Oct3Al (t½ ∼200 s, up to 7 exchanges). The exchanges are reversible and the methyl groups on the cation are also observed to exchange with the added R3Al species. These results point to the reactive components of MAO having a structure that deviates significantly from the cage-like motifs studied to date.

Graphical abstract: Modifying methylalumoxane via alkyl exchange

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Publication details

The article was received on 24 Oct 2018, accepted on 20 Nov 2018 and first published on 21 Nov 2018


Article type: Paper
DOI: 10.1039/C8DT04242J
Citation: Dalton Trans., 2018,47, 17291-17298
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    Modifying methylalumoxane via alkyl exchange

    H. S. Zijlstra, A. Joshi, M. Linnolahti, S. Collins and J. S. McIndoe, Dalton Trans., 2018, 47, 17291
    DOI: 10.1039/C8DT04242J

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