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dc.contributor.authorPino Chamorro, José Ángel
dc.contributor.authorBeltrán Álvarez, Tomás Francisco
dc.contributor.authorFernández-Trujillo Rey, María Jesús
dc.contributor.authorBasallote, Manuel G.
dc.contributor.authorLlusar, Rosa
dc.contributor.authorAlgarra, Andrés G.
dc.date.accessioned2018-04-23T09:35:01Z
dc.date.available2018-04-23T09:35:01Z
dc.date.issued2017-11-24
dc.identifier.citationPINO CHAMORRO, José Ángel; BELTRÁN ÁLVAREZ, Tomás Francisco; FERNÁNDEZ-TRUJILLO, María Jesús; BASALLOTE, Manuel G.; LLUSAR, Rosa; ALGARRA, Andrés G. Studies on the Reactivity of the Aminophosphino [W 3 S 4 Br 3 (edpp ) 3 ] + (edpp= (2 - aminoethyl) diphenylphosphine) Cluster Cation towards Bases Reveal ing a Non - Passive Role of the Amino Group. European Journal of Inorganic Chemistry (2017), issue 43, p. 5006-5014ca_CA
dc.identifier.urihttp://hdl.handle.net/10234/174270
dc.description.abstractDetailed studies using stopped-flow, 31 P{ 1 H} NMR, a nd ESI - MS have been carried on the reaction of the [W 3 S 4 Br 3 (edpp) 3 ] + (edpp = ( 2 - aminoethyl)diphenylphosphine ) cluster with NaOH and Et 3 N in acetonitrile. The study has allowed identification of h ydroxo species during the reactivity studies an d the development of a procedure for the synthesis of the [W 3 S 4 (OH) 3 (edpp) 3 ] + cluster in high yields. This involves the substitution of the coordinated bromides by OH - ligands, and the associated kinetics is several orders of magnitude faster than that with Cl - , F - , and SCN - anions. The reactivity with Et 3 N is quite different and essentially leads to the formation of species resulting from proton abstraction at the NH 2 groups of the edpp ligands, the amine acting as a base. DFT calculations provide a rationalization of the experimental findings by showing that Et 3 N coordination does not occur even in the presence of a vacant coordination site. Computed pKa values for the different species involved in these reactions indicate the possibility of proton exchange between the NH 2 groups of edpp and Et 3 N, which is confirmed by the NMR and ESI - MS data. The formation of intermediate cluster species containing the conjugate base o f edpp has been also found to facilitate bromide dissociation, thus providing a reaction pathway with a lower energy barrier that justifies the faster formation of [W 3 S 4 (OH) 3 (edpp) 3 ] + with respect to other [W 3 S 4 X 3 (edpp) 3 ] + (X= Cl, F, SCN) clusters.ca_CA
dc.format.extent10 p.ca_CA
dc.format.mimetypeapplication/pdfca_CA
dc.language.isoengca_CA
dc.publisherWileyca_CA
dc.relation.isPartOfEuropean Journal of Inorganic Chemistry (2017), issue 43ca_CA
dc.subjectClusterca_CA
dc.subjectAminophosphino ligandca_CA
dc.subjectKineticsca_CA
dc.subjectReaction mechanismsca_CA
dc.titleStudies on the Reactivity of the Aminophosphino [W 3 S 4 Br 3 (edpp ) 3 ] + (edpp= (2 - aminoethyl) diphenylphosphine) Cluster Cation towards Bases Reveal ing a Non - Passive Role of the Amino Groupca_CA
dc.typeinfo:eu-repo/semantics/articleca_CA
dc.identifier.doihttps://doi.org/10.1002/ejic.201700641
dc.relation.projectIDThe financial support of the Spanish Ministerio de Economía y Competividad and FEDER funds (Project Nos. CTQ2015 - 65707 - C2 - 2 - P and CTQ2015 - 65207 - P) is gratefully acknowledged.ca_CA
dc.rights.accessRightsinfo:eu-repo/semantics/openAccessca_CA
dc.relation.publisherVersionhttps://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.201700641ca_CA
dc.type.versioninfo:eu-repo/semantics/publishedVersionca_CA


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