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dc.contributor.authorCalvo-Losada, Saturnino
dc.contributor.authorChávez, Miriam
dc.contributor.authorQuirante, José-Joaquín
dc.date.accessioned2015-06-16T08:43:26Z
dc.date.available2015-06-16T08:43:26Z
dc.date.created2015
dc.date.issued2015-06-16
dc.identifier.urihttp://hdl.handle.net/10630/9915
dc.description.abstractThis study constitutes an extension of a previous research on the regioselectivity of the copper catalyzed cycloaddition of azides to alkynes (1) (the CuAAC reaction) by Quantum Chemical Topological methods. In particular, by following the evolution the topology of the laplacian of the electronic charge density and its gradient vector field along the reaction coordinates, computed with different Density Functionals (B3LYP, LCwPBE, M06-L, wB97XD, and M06-2X) and 6-311++G(d,p) basis set. For the mononuclear process, we found that a H-type interaction conditions the attack of the azide in the 1,5-CuAAC. In addition, given that experimental evidences (2) seem to suggest the participation of a second Cu atom in the reaction coordinate, we have explored very recently (3) the mechanism involving a dinuclear copper cluster at the LCwPBE/6-311++G(d,p) level. Interestingly, the catalyst modifies the uncatalyzed Huisgen mechanism, by inducing sequentially first the terminal N-C bond and the internal afterwards in a concerted fashion for the 1,4-CuAAC and stepwise for the 1,4-Cu2AAC. Furthermore, as seen in the topology of the laplacian, the catalyst provoked that a carbon acts as a nucleophile and turned pericyclic mechanism into pseudopericyclic (3). [1] Calvo-Losada S., Pino M.S. and Quirante J.J., J. Mol.Model., 20, 2187 (2014) [2] Worrell B. T., Malik J. A. and Fokin V. V., Science, 340, 457 (2013) [3] Calvo-Losada S., Pino M.S. and Quirante J.J., J. Phys.Chem. B, 119,1243 (2015)es_ES
dc.description.sponsorshipUniversidad de Málaga. Campus de Excelencia Internacional Andalucía Tech.es_ES
dc.language.isoenges_ES
dc.rightsinfo:eu-repo/semantics/openAccesses_ES
dc.subjectQuímica cuánticaes_ES
dc.subject.otherClick Chemistryes_ES
dc.subject.otherDFTes_ES
dc.subject.otherTransition Stateses_ES
dc.titleExploring the regioselectivity for the cycloaddition of azides to alkynes catalyzed by dinuclear copper clusters (Cu2AAC) with the topology of 2rho(r) and 2rho(r)es_ES
dc.typeinfo:eu-repo/semantics/conferenceObjectes_ES
dc.centroFacultad de Cienciases_ES
dc.relation.eventtitleThe 15th ICQC (International Congress of Quantum Chemistry)es_ES
dc.relation.eventplaceBeijing (CHINA)es_ES
dc.relation.eventdate08/06/2015es_ES
dc.identifier.orcidhttp://orcid.org/0000-0003-1040-989Xes_ES
dc.cclicenseby-nc-ndes_ES


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