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Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach
dc.contributor.author | Pino Chamorro, Jose Angel | |
dc.contributor.author | Laricheva, Yuliya A. | |
dc.contributor.author | Guillamón, Eva | |
dc.contributor.author | Fernández-Trujillo, M. Jesús | |
dc.contributor.author | Bustelo, Emilio | |
dc.contributor.author | Gushchin, Artem L. | |
dc.contributor.author | Shmelev, Nikita Y. | |
dc.contributor.author | Abramov, Pavel A. | |
dc.contributor.author | Sokolov, Maxim | |
dc.contributor.author | Llusar, Rosa | |
dc.contributor.author | García Basallote, Manuel | |
dc.contributor.author | Algarra, Andrés G. | |
dc.date.accessioned | 2016-11-23T14:57:22Z | |
dc.date.available | 2016-11-23T14:57:22Z | |
dc.date.issued | 2016 | |
dc.identifier.issn | 1144-0546 | |
dc.identifier.issn | 1369-9261 | |
dc.identifier.uri | http://hdl.handle.net/10234/164645 | |
dc.description.abstract | A heterocyclic ligand 4,4′-di-tert-butyl-2,2′-bipyridine (dbbpy) has been coordinated to the Mo3S4 cluster unit affording the complex [Mo3S4Cl3(dbbpy)3]+ ([1]+) in a one-step ligand-exchange protocol from [Mo3S4(tu)8(H2O)]Cl4·4H2O (tu = thiourea). The new cluster was isolated as [1]PF6 and [1]Cl salts in high yields and the crystal structure of the latter determined by X-ray analysis. The synthetic procedure was extended to tungsten to afford [W3S4Cl3(dbbpy)3]+ ([2]+). Kinetic and NMR studies show that [1]+ reacts with several alkynes to form dithiolene species via concerted [3+2] cycloaddition reactions whereas [2]+ remains inert under similar conditions. The different rates for the reactions of [1]+ are rationalised by computational (DFT) calculations, which show that the more electron-withdrawing the substituents of the alkyne the faster the reaction. The inertness of [2]+ is due to the endergonicity of its reactions, which feature ΔGr values systematically 5–7 kcal mol−1 more positive than for those of [1]+. | ca_CA |
dc.description.sponsorShip | Financial support of the Russian Foundation for Basic Research (grant 15-03-02775) is gratefully acknowledged. Financial support of the Spanish Ministerio de Economia y Competitividad and FEDER funds from the European Union (grants CTQ2015-65707-C2-2-P and CTQ2015-65207-P), Universitat Jaume I (research project P1.1B2013-40) and Generalitat Valenciana (PrometeoII/2014/022) is gratefully acknowledged. | ca_CA |
dc.format.extent | 9 p. | ca_CA |
dc.format.mimetype | application/pdf | ca_CA |
dc.language.iso | eng | ca_CA |
dc.publisher | Royal Society of Chemistry | ca_CA |
dc.relation.isPartOf | New J. Chem., 2016, 40, 7872--7880 | ca_CA |
dc.rights | This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016. PINO-CHAMORRO, Jose A., et al. Cycloaddition of alkynes to diimino Mo 3 S 4 cubane-type clusters: a combined experimental and theoretical approach. New Journal of Chemistry, 2016, vol. 40, no 9, p. 7872-7880. Http://dx.doi.org/10.1039/c6nj01787h. - Reproduced by permission of The Royal Society of Chemistry. | ca_CA |
dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | * |
dc.title | Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach | ca_CA |
dc.type | info:eu-repo/semantics/article | ca_CA |
dc.identifier.doi | http://dx.doi.org/10.1039/c6nj01787h | |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | ca_CA |
dc.relation.publisherVersion | http://pubs.rsc.org/en/content/articlelanding/2016/nj/c6nj01787h#!divAbstract | ca_CA |
dc.type.version | info:eu-repo/semantics/acceptedVersion | ca_CA |
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