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dc.contributor.authorBoutland, Aaron J.
dc.contributor.authorLamsfus, Carlos A.
dc.contributor.authorMaitland, Brant
dc.contributor.authorMaron, Laurent
dc.contributor.authorStasch, Andreas
dc.contributor.authorJones, Cameron
dc.date.accessioned2018-09-05T23:35:27Z
dc.date.available2018-09-05T23:35:27Z
dc.date.issued2017-10-09
dc.identifier.citationBoutland , A J , Lamsfus , C A , Maitland , B , Maron , L , Stasch , A & Jones , C 2017 , ' Accessing stable magnesium acyl compounds : reductive cleavage of esters by magnesium(I) dimers ' Chemistry - A European Journal , vol. 23 , no. 56 , pp. 14049-14055 . https://doi.org/10.1002/chem.201703061en
dc.identifier.issn0947-6539
dc.identifier.otherPURE: 250899478
dc.identifier.otherPURE UUID: 176ee979-7f27-47ac-a081-3e39393ddbb1
dc.identifier.otherScopus: 85028917113
dc.identifier.otherORCID: /0000-0002-7407-8287/work/58055964
dc.identifier.urihttp://hdl.handle.net/10023/15974
dc.descriptionC.J. and A.S. thank the Australian Research Council for financial support. C.J. also thanks the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043).en
dc.description.abstractThe first examples of magnesium acyls, [(Nacnac)Mg{μ-C(Ph)O}(μ-OR)Mg(Nacnac)] (R = Me, But or Ph; Nacnac = [HC(MeCNAr)2]-; Ar = C6H2Me3-2,4,6 (MesNacnac), C6H3Et2-2,6 (DepNacnac), C6H3Pri2-2,6 (DipNacnac)), have been prepared by reductive cleavage of a series of esters using dimeric magnesium(I) reducing agents, [{(Nacnac)Mg}2]. Crystallographic studies reveal the complexes to be dimeric, being bridged by both phenyl-acyl and alkoxide/aryloxide fragments. The crystal structures, combined with results of spectroscopic and computational studies suggest that the nature of the acyl ligands within these complexes should be viewed as lying somewhere between anionic umpolung acyl and oxo-carbene. However, reactions of the acyl complexes with a variety of organic electrophiles did not provide evidence of umpolung acyl reactivity. A number of attempts to prepare alkoxide free magnesium acyls were carried out, and while these were unsuccessful, they did lead to unusual products, the crystallographic and spectroscopic details of which are discussed.
dc.language.isoeng
dc.relation.ispartofChemistry - A European Journalen
dc.rights© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with the publisher’s policies. This is the author created accepted version manuscript following peer review and as such may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/chem.201703061en
dc.subjectMagnesium acylen
dc.subjectMagnesium(I)en
dc.subjectEster cleavageen
dc.subjectReductionen
dc.subjectUmpolungen
dc.subjectQD Chemistryen
dc.subjectNDASen
dc.subject.lccQDen
dc.titleAccessing stable magnesium acyl compounds : reductive cleavage of esters by magnesium(I) dimersen
dc.typeJournal articleen
dc.description.versionPostprinten
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.identifier.doihttps://doi.org/10.1002/chem.201703061
dc.description.statusPeer revieweden
dc.date.embargoedUntil2018-09-06
dc.identifier.urlhttp://onlinelibrary.wiley.com/doi/10.1002/chem.201703061/full#footer-support-infoen


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