Unique distal size selectivity with a digold catalyst during alkyne homocoupling
| dc.contributor.affiliation | Instituto Universitario Mixto de Tecnología Química | |
| dc.contributor.author | Leyva Perez, Antonio | |
| dc.contributor.author | Domenech Carbo, Antonio | es_ES |
| dc.contributor.author | Corma Canós, Avelino | |
| dc.contributor.funder | Ministerio de Ciencia e Innovación | es_ES |
| dc.contributor.funder | Generalitat Valenciana | es_ES |
| dc.date.accessioned | 2016-05-13T10:20:20Z | |
| dc.date.available | 2016-05-13T10:20:20Z | |
| dc.date.issued | 2015-04 | |
| 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.accrualMethod | S | 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 |
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| 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.description.volume | 6 | es_ES |
| dc.identifier.doi | 10.1038/ncomms7703 | |
| dc.identifier.issn | 2041-1723 | |
| dc.identifier.uri | https://riunet.upv.es/handle/10251/64023 | |
| dc.language | Inglés | es_ES |
| dc.publisher | Nature Publishing Group | es_ES |
| dc.relation.ispartof | Nature Communications | es_ES |
| 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 |
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| dc.relation.senia | 309489 | es_ES |
| dc.rights | Reserva de todos los derechos | es_ES |
| dc.rights.accessRights | Abierto | 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.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
| dspace.entity.type | Publication | |
| person.identifier | 250316 | |
| person.identifier | 180535 | |
| person.identifier.orcid | 0000-0003-1063-5811 | |
| person.identifier.orcid | 0000-0002-2232-3527 | |
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