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http://hdl.handle.net/10261/154875
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dc.contributor.author | Iturmendi, Amaia | - |
dc.contributor.author | Sanz Miguel, Pablo J. | - |
dc.contributor.author | Popoola, Saheed A. | - |
dc.contributor.author | Al-Saadi, Abdulaziz A. | - |
dc.contributor.author | Iglesias, Manuel | - |
dc.contributor.author | Oro, Luis A. | - |
dc.date.accessioned | 2017-09-07T11:38:30Z | - |
dc.date.available | 2017-09-07T11:38:30Z | - |
dc.date.issued | 2016 | - |
dc.identifier | doi: 10.1039/C6DT03010F | - |
dc.identifier | e-issn: 1477-9234 | - |
dc.identifier | issn: 1477-9226 | - |
dc.identifier.citation | Dalton Transactions 45(42): 16955-16965 (2016) | - |
dc.identifier.uri | http://hdl.handle.net/10261/154875 | - |
dc.description.abstract | A variety of binuclear rhodium(i) complexes featuring two bridging dimethylphosphinate ligands ((CH)PO ) have been prepared and tested in the alkoxycarbonylation of aromatic C-H bonds. The complex [Rh(μ-κO,O′-(CH)PO)(cod)] has been prepared by a reaction of [Rh(μ-MeO)(cod)] with 2 equivalents of dimethylphosphinic acid. Binuclear complexes [Rh(μ-κO,O′-(CH)PO)(CO)L] (L = PPh, P(OMe)Ph and P(OPh)) were obtained by carbonylation of the related mononuclear complexes [Rh(κO-(CH)PO)(cod)(L)], which were prepared in situ by the reaction of [Rh(μ-κO,O′-(CH)PO)(cod)] with 2 equivalents of L. Conversely, if L = IPr, the reaction of [Rh(μ-κO,O′-(CH)PO)(CO)L] with carbon monoxide affords the mononuclear complex [Rh(κO-(CH)PO)(CO)IPr]. The subsequent reaction with trimethylamine N-oxide gives the corresponding binuclear complex [Rh(μ-κO,O′-(CH)PO)(CO)(IPr)] by abstraction of one of the carbonyl ligands. Complexes [Rh(μ-κO,O′-(CH)PO)(cod)] and [Rh(κO-(CH)PO)(cod)(L)] (L = IPr, PPh, P(OMe)Ph, P(OPh)) are active precatalysts in the alkoxycarbonylation of C-H bonds, with the ligand system playing a key role in the catalytic activity. The complexes that feature more labile Rh-L bonds give rise to better catalysts, probably due to the more straightforward substitution of L by a second carbonyl ligand, since a more electrophilic carbonyl carbon atom is more susceptible toward aryl migration. In fact, complexes [Rh(μ-κO,O′-(CH)PO)(CO)] and [Rh(μ-Cl)(CO)], generated in situ from [Rh(μ-κO,O′-(CH)PO)(cod)] and [Rh(μ-Cl)(cod)], respectively, are the most active catalysts tested in this work. | - |
dc.description.sponsorship | The support of KFUPM (KAST-funded project ART-32-68) and the KFUPM-University of Zaragoza research agreement is highly appreciated. This work was further supported by the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) (CONSOLIDER INGENIO CSD2009-0050) and the Diputación General de Aragón (DGA/FSE-E07). | - |
dc.publisher | Royal Society of Chemistry (UK) | - |
dc.rights | closedAccess | - |
dc.title | Dimethylphosphinate bridged binuclear Rh(I) catalysts for the alkoxycarbonylation of aromatic C-H bonds | - |
dc.type | artículo | - |
dc.identifier.doi | 10.1039/C6DT03010F | - |
dc.date.updated | 2017-09-07T11:38:30Z | - |
dc.description.version | Peer Reviewed | - |
dc.language.rfc3066 | eng | - |
dc.contributor.funder | King Fahd University of Petroleum and Minerals | - |
dc.contributor.funder | Universidad de Zaragoza | - |
dc.contributor.funder | European Commission | - |
dc.contributor.funder | Ministerio de Economía y Competitividad (España) | - |
dc.contributor.funder | Diputación General de Aragón | - |
dc.relation.csic | Sí | - |
dc.identifier.funder | http://dx.doi.org/10.13039/501100004055 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100007041 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100000780 | es_ES |
dc.identifier.funder | http://dx.doi.org/10.13039/501100003329 | es_ES |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.openairetype | artículo | - |
item.grantfulltext | none | - |
item.cerifentitytype | Publications | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.fulltext | No Fulltext | - |
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