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dc.contributor.authorGarcía Algarra, Andrés
dc.contributor.authorPino-Chamorro, Jose Ángel
dc.contributor.authorA. Laricheva, Yuliya
dc.contributor.authorGuillamón, Eva
dc.contributor.authorFernández-Trujillo Rey, María Jesús
dc.contributor.authorBustelo, Emilio
dc.contributor.authorL. Gushchin, Artem
dc.contributor.authorY. Shmelev, Nikita
dc.contributor.authorA. Abramov, Pavel
dc.contributor.authorN. Sokolov, Maxim
dc.contributor.authorLlusar, Rosa
dc.contributor.authorGarcía Basallote, Manuel
dc.contributor.otherCiencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánicaen_US
dc.date.accessioned2018-05-11T11:25:23Z
dc.date.available2018-05-11T11:25:23Z
dc.date.issued2016
dc.identifier.urihttp://hdl.handle.net/10498/20490
dc.description.abstractA heterocyclic ligand 4,40-di-tert-butyl-2,20-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 DGr values systematically 5–7 kcal mol 1 more positive than for those of [1]+.en_US
dc.formatapplication/pdfen_US
dc.language.isoengen_US
dc.publisherThe Royal Society of Chemistry and Owner Societiesen_US
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internacional*
dc.rightsinfo:eu-repo/semantics/openAccess
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.sourceNew Journal of Chemistry 2016, 40, 7872--7880en_US
dc.titleCycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approachen_US
dc.typeinfo:eu-repo/semantics/articleen_US
dc.identifier.doi10.1039/c6nj01787h


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Attribution-NonCommercial-NoDerivatives 4.0 Internacional
This work is under a Creative Commons License Attribution-NonCommercial-NoDerivatives 4.0 Internacional