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dc.contributor.authorCrawford, Luke
dc.contributor.authorCole-Hamilton, David John
dc.contributor.authorBuehl, Michael
dc.identifier.citationCrawford , L , Cole-Hamilton , D J & Buehl , M 2015 , ' Uncovering the mechanism of homogeneous methyl methacrylate formation with P,N chelating ligands and palladium : favored reaction channels and selectivities ' , Organometallics , vol. 34 , no. 2 , pp. 438–449 .
dc.identifier.otherPURE: 159997620
dc.identifier.otherPURE UUID: 78f184c9-0c37-4e6d-8f14-0a9741e8acf5
dc.identifier.otherWOS: 000348619700006
dc.identifier.otherScopus: 84921695015
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131805
dc.descriptionThe authors would like to thank the University of St. Andrews School of Chemistry and EaStCHEM for supporten
dc.description.abstractThe catalytic alkoxycarbonylation of alkynes via palladium and P,N ligands, studied through a prototypical reaction involving propyne methoxycarbonylation yielding methyl methacrylate, has been explored at the B3PW91-D3/PCM level of density functional theory. Four different reaction routes have been probed in detail, spanning those involving one or two hemilabile P,N ligands and either hydride or carbomethoxy mechanisms. The cycle that is both energetically most plausible and congruent with experimental data involves Pd(0) and two P,N ligands acting co-catalytically in turn to shuffle protons via both protonation and deprotonation reactions. Other mechanisms proposed in the literature can be discounted because they would lead to insurmountable barriers or incorrect selectivities. For the preferred mechanism, the P,N ligand is found to be crucial in determining the strong regioselectivity and intrinsically controls the overall turnover of the catalytic cycle with moderate barriers (ΔG‡ of 20.1 to 22.9 kcal/mol) predicted. Furthermore, the necessary acidic conditions are rationalized via a potential dicationic channel.
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society, after peer review and technical editing by the publisher. To access the final edited and published work see
dc.subjectQD Chemistryen
dc.titleUncovering the mechanism of homogeneous methyl methacrylate formation with P,N chelating ligands and palladium : favored reaction channels and selectivitiesen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.description.statusPeer revieweden

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