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Unique distal size selectivity with a digold catalyst during alkyne homocoupling

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Unique distal size selectivity with a digold catalyst during alkyne homocoupling

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dc.contributor.author Leyva Perez, Antonio es_ES
dc.contributor.author Domenech Carbo, Antonio es_ES
dc.contributor.author Corma Canós, Avelino es_ES
dc.date.accessioned 2016-05-13T10:20:20Z
dc.date.available 2016-05-13T10:20:20Z
dc.date.issued 2015-04
dc.identifier.issn 2041-1723
dc.identifier.uri http://hdl.handle.net/10251/64023
dc.description.abstract Metal-catalysed chemical reactions are often controlled by steric hindrance around the metal atom and it is rare that substituents far away of the reaction site could be differentiated during reaction, particularly if they are simple alkyl groups. Here we show that a gold catalyst is able to discriminate between linear carbon alkynes with 10 or 12 atoms in the chain during the oxidative homocoupling of alkynes: the former is fully reactive and the latter is practically unreactive. We present experimental evidences, which support that the distal size selectivity occurs by the impossibility of transmetallating two long alkyl chains in an A-framed, mixed-valence digold (I, III) acetylide complex. We also show that the reductive elimination of two alkyne molecules from a single Au(III) atom occurs extremely fast, in <1 min at -78 degrees C (turnover frequency > 0.016 s(-1)). es_ES
dc.description.sponsorship Financial support by Consolider-Ingenio 2010 (proyecto MULTICAT) and Severo Ochoa programs from MCIINN and Prometeo program from Generalitat Valenciana is acknowledged. A. L.-P. thanks ITQ for the concession of a contract. We thank Dr J.A. Vidal for assistance with the low-temperature NMR experiments, and Dr M. Boronat for the DFT calculations. en_EN
dc.language Inglés es_ES
dc.publisher Nature Publishing Group es_ES
dc.relation.ispartof Nature Communications es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject HOMOGENEOUS GOLD CATALYSIS es_ES
dc.subject C-H ACTIVATION es_ES
dc.subject TERMINAL ALKYNES es_ES
dc.subject COUPLING REACTIONS es_ES
dc.subject COMPLEXES es_ES
dc.subject TRANSMETALATION es_ES
dc.subject ALKENES es_ES
dc.subject CYCLIZATION es_ES
dc.subject GOLD(III) es_ES
dc.subject ACETYLIDE es_ES
dc.subject.classification QUIMICA ORGANICA es_ES
dc.title Unique distal size selectivity with a digold catalyst during alkyne homocoupling es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1038/ncomms7703
dc.relation.projectID info:eu-repo/grantAgreement/MICINN//CSD2009-00050/ES/Desarrollo de catalizadores más eficientes para el diseño de procesos químicos sostenibles y produccion limpia de energia/ / es_ES
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Departamento de Química - Departament de Química es_ES
dc.contributor.affiliation Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química es_ES
dc.description.bibliographicCitation Leyva Perez, A.; Domenech Carbo, A.; Corma Canós, A. (2015). Unique distal size selectivity with a digold catalyst during alkyne homocoupling. Nature Communications. 6. https://doi.org/10.1038/ncomms7703 es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion http://dx.doi.org/10.1038/ncomms7703 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 6 es_ES
dc.relation.senia 309489 es_ES
dc.contributor.funder Ministerio de Ciencia e Innovación es_ES
dc.contributor.funder Generalitat Valenciana es_ES
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