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dc.contributor.authorHong, Miao
dc.contributor.authorTang, Xiaoyan
dc.contributor.authorFalivene, Laura
dc.contributor.authorCaporaso, Lucia
dc.contributor.authorCavallo, Luigi
dc.contributor.authorChen, Eugene Y.-X.
dc.date.accessioned2016-01-24T10:26:13Z
dc.date.available2016-01-24T10:26:13Z
dc.date.issued2016-02-02
dc.identifier.citationProton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters 2016 Journal of the American Chemical Society
dc.identifier.issn0002-7863
dc.identifier.issn1520-5126
dc.identifier.doi10.1021/jacs.5b13019
dc.identifier.urihttp://hdl.handle.net/10754/594735
dc.description.abstractThis contribution presents a full account of experimental and theoretical/computational investigations into the N-heterocyclic carbene (NHC)-catalyzed proton-transfer polymerization (HTP) that converts common dimethacrylates (DMAs) containing no protic groups into unsaturated polyesters. This new HTP proceeds through the step-growth propagation cycles via enamine intermediates, consisting of the proposed conjugate addition–proton transfer–NHC release fundamental steps. This study examines the monomer and catalyst scopes as well as the fundamental steps involved in the overall HTP mechanism. DMAs having six different types of linkages connecting the two methacrylates have been polymerized into the corresponding unsaturated polyesters. The most intriguing unsaturated polyester of the series is that based on the biomass-derived furfuryl dimethacrylate, which showed a unique self-curing ability Four MeO– and Cl–substituted TPT (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene) derivatives as methanol insertion products, RxTPT(MeO/H) (R = MeO, Cl; x = 2, 3), and two free carbenes (catalysts), OMe2TPT and OMe3TPT, have been synthesized, while OMe2TPT(MeO/H) and OMe2TPT have also been structurally characterized. The structure/reactivity relationship study revealed that OMe2TPT, being both a strong nucleophile and a good leaving group, exhibits the highest HTP activity and also produced the polyester with the highest Mn, while the Cl–substituted TPT derivatives are least active and efficient. Computational studies have provided mechanistic insights into the tail-to-tail dimerization coupling step as a suitable model for the propagation cycle of the HTP. The extensive energy profile was mapped out and the experimentally observed unicity of the TPT-based catalysts was satisfactorily explained with the thermodynamic formation of key spirocyclic species.
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttp://pubs.acs.org/doi/10.1021/jacs.5b13019
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/10.1021/jacs.5b13019.
dc.titleProton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalJournal of the American Chemical Society
dc.eprint.versionPost-print
dc.contributor.institutionDepartment of Chemistry, Colorado State University, Fort Collins, Colorado 80523-1872, USA
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Papa Paolo Giovanni II, I-84084, Fisciano, Italy
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)
kaust.personFalivene, Laura
kaust.personCavallo, Luigi
dc.relation.issupplementedbyDOI:10.5517/cc1kchv8
dc.relation.issupplementedbyDOI:10.5517/cc1kchxb
refterms.dateFOA2017-01-18T00:00:00Z
display.relations<b> Is Supplemented By:</b> <br/> <ul><li><i>[Dataset]</i> <br/> Hong, M., Tang, X., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016). CCDC 1441030: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1kchv8. DOI: <a href="https://doi.org/10.5517/cc1kchv8">10.5517/cc1kchv8</a> HANDLE: <a href="http://hdl.handle.net/10754/624488">10754/624488</a></li><li><i>[Dataset]</i> <br/> Hong, M., Tang, X., Falivene, L., Caporaso, L., Cavallo, L., & Chen, E. Y.-X. (2016). CCDC 1441032: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1kchxb. DOI: <a href="https://doi.org/10.5517/cc1kchxb">10.5517/cc1kchxb</a> HANDLE: <a href="http://hdl.handle.net/10754/624489">10754/624489</a></li></ul>
dc.date.published-online2016-02-02
dc.date.published-print2016-02-17


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