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dc.contributor.authorWalton, John Christopher
dc.contributor.authorBencivenni, G.
dc.contributor.authorCesari, R.
dc.contributor.authorNanni, D.
dc.contributor.authorEl Mkami, Hassane
dc.date.accessioned2013-12-04T15:31:05Z
dc.date.available2013-12-04T15:31:05Z
dc.date.issued2010-09
dc.identifier.citationWalton , J C , Bencivenni , G , Cesari , R , Nanni , D & El Mkami , H 2010 , ' EPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichlorides ' Beilstein Journal of Organic Chemistry , vol. 6 , pp. 713-725 . https://doi.org/10.3762/bjoc.6.84en
dc.identifier.issn1860-5397
dc.identifier.otherPURE: 9854257
dc.identifier.otherPURE UUID: c95d2c3e-bd8c-4ef1-b86f-e4210fd28e9b
dc.identifier.otherScopus: 77958516544
dc.identifier.otherORCID: /0000-0003-2746-6276/work/56638852
dc.identifier.otherORCID: /0000-0002-0552-5784/work/60195415
dc.identifier.urihttp://hdl.handle.net/10023/4263
dc.description.abstractThe reactions of group 13 metal trichlorides with aromatic azides were examined by CW EPR and pulsed ENDOR spectroscopies. Complex EPR spectra were obtained from reactions of aluminium, gallium and indium trichlorides with phenyl azides containing a variety of substituents. Analysis of the spectra showed that 4-methoxy-, 3-methoxy- and 2-methoxyphenyl azides all gave ‘dimer’ radical cations [ArNHC6H4NH2]+• and trimers [ArNHC6H4NHC6H4NH2]+• followed by polymers. 4-Azidobenzonitrile, with its electron-withdrawing substituent, did not react. In general the aromatic azides appeared to react most rapidly with AlCl3 but this reagent tended to generate much polymer. InCl3 was the least reactive group 13 halide. DFT computations of the radical cations provided corroborating evidence and suggested that the unpaired electrons were accommodated in extensive π-delocalised orbitals. A mechanism to account for the reductive conversion of aromatic azides to the corresponding anilines and thence to the dimers and trimers is proposed
dc.language.isoeng
dc.relation.ispartofBeilstein Journal of Organic Chemistryen
dc.rights© 2010 Bencivenni et al; licensee Beilstein-Institut. This is an Open Access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: (http://www.beilstein-journals.org/bjoc)en
dc.subjectAluminiumen
dc.subjectAromatic azidesen
dc.subjectENDORen
dc.subjectEPRen
dc.subjectGalliumen
dc.subjectIndiumen
dc.subjectQD Chemistryen
dc.subject.lccQDen
dc.titleEPR and pulsed ENDOR study of intermediates from reactions of aromatic azides with group 13 metal trichloridesen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.School of Physics and Astronomyen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.3762/bjoc.6.84
dc.description.statusPeer revieweden


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