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Lookup NU author(s): Christopher Beattie, Professor Michael North
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The bimetallic aluminium(salen) complex [(Al(salen))(2)O] is known to catalyse the reaction between epoxides and heterocumulenes (carbon dioxide, carbon disulfide and isocyanates) leading to five-membered ring heterocycles. Despite their apparent similarities, these three reactions have very different mechanistic features, and a kinetic study of oxazolidinone synthesis combined with previous kinetic work on cyclic carbonate and cyclic dithiocarbonate synthesis showed that all three reactions follow different rate equations. An NMR study of [Al(salen)](2)O and phenylisocyanate provided evidence for an interaction between them, consistent with the rate equation data. A variable-temperature kinetics study on all three reactions showed that cyclic carbonate synthesis had a lower enthalpy of activation and a more negative entropy of activation than the other two heterocycle syntheses. The kinetic study was extended to oxazolidinone synthesis catalysed by the monometallic complex Al(salen) Cl, and this reaction was found to have a much less negative entropy of activation than any reaction catalysed by [Al(salen)](2)O, a result that can be explained by the partial dissociation of an oligomeric Al(salen) Cl complex. A mechanistic rationale for all of the results is presented in terms of [Al(salen)](2)O being able to function as a Lewis acid and/or a Lewis base, depending upon the susceptibility of the heterocumulene to reaction with nucleophiles.
Author(s): Beattie C, North M
Publication type: Article
Publication status: Published
Journal: Chemistry - A European Journal
Year: 2014
Volume: 20
Issue: 26
Pages: 8182-8188
Print publication date: 23/06/2014
Online publication date: 13/05/2014
Acceptance date: 01/02/2014
ISSN (print): 0947-6539
ISSN (electronic): 1521-3765
Publisher: Wiley - VCH Verlag GmbH & Co. KGaA
URL: http://dx.doi.org/10.1002/chem.201400007
DOI: 10.1002/chem.201400007
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