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Mechanistic investigation of the reaction of epoxides with heterocumulenes catalysed by a bimetallic aluminium salen complex

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JournalChemistry - A European Journal
DateE-pub ahead of print - 13 May 2014
DatePublished (current) - 23 Jun 2014
Issue number26
Volume20
Number of pages7
Pages (from-to)8182-8188
Early online date13/05/14
Original languageEnglish

Abstract

The bimetallic aluminium(salen) complex [(Al(salen))2O] 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)]2O 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)]2O, 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)]2O being able to function as a Lewis acid and/or a Lewis base, depending upon the susceptibility of the heterocumulene to reaction with nucleophiles. One ring to rule them all: Kinetic studies on the reaction of epoxides with carbon dioxide, carbon disulfide, and phenylisocyanate catalyzed by [Al(salen)]2O provide an overarching mechanistic understanding of these reactions, which follow three different rate equations (see scheme). The results highlight the potential of [Al(salen)]2O to act as both a Lewis acid and a Lewis base with the relative importance of these determined by the heterocumulene.

    Research areas

  • aluminium, carbon dioxide, carbon disulfide, epoxides, kinetics, reaction mechanisms, ring-opening

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