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http://hdl.handle.net/10261/19260
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Campo DC | Valor | Lengua/Idioma |
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dc.contributor.author | Baya, Miguel | - |
dc.contributor.author | Eguillor, Beatriz | - |
dc.contributor.author | Esteruelas, Miguel A. | - |
dc.contributor.author | Lledós, Agustí | - |
dc.contributor.author | Oliván, Montserrat | - |
dc.contributor.author | Oñate, Enrique | - |
dc.date.accessioned | 2009-12-02T10:54:37Z | - |
dc.date.available | 2009-12-02T10:54:37Z | - |
dc.date.issued | 2007-09 | - |
dc.identifier.citation | Organometallics 26(21): 5140-5152 (2007) | en_US |
dc.identifier.issn | 0276-7333 | - |
dc.identifier.uri | http://hdl.handle.net/10261/19260 | - |
dc.description | 13 pages, 1 table, 13 figures, 4 schemes.-- Supporting Information Available: http://pubs.acs.org. | en_US |
dc.description.abstract | The hexahydride complex OsH6(PiPr3)2 (1) reacts with 8-methylquinoline and 2-(dimethylamino)pyridine to give OsH3(CH2C9H6N)(PiPr3)2 (2) and OsH3{CH2N(CH3)-o-C5H4N}(PiPr3)2 (3), respectively, as a result of the release of two hydrogen molecules of 1 and the C(sp3)-H bond activation of a methyl group of the organic substrates. In solution the hydride ligands and the hydrogen atoms of the methylene group of 2 exchange their positions. The activation parameters for the process are ¢Hq ) 18.9 ( 0.1 kcalâmol-1 and ¢Sq ) 3 ( 2 eu. Treatment of 2 with HBF4 affords the hydride-elongated dihydrogen derivative [OsH(è2-H2)(CH3C9H6N)(PiPr3)2]BF4 (6), with the methyl group of the quinoline ligand coordinated in a è3-H2C fashion. The X-ray structure of 6 and the DFT optimization of the structure of the model cation [OsH(è2-H2)(CH4)(NH3)(PMe3)2]+ prove that the methyl coordination in the ä agostic complex is similar to the methane coordination in the model compound. The reaction of 3 with HBF4 leads to the cyclic carbene derivative [OsH3{dCHN(CH3)-o-C5H4N}(PiPr3)2]BF4 (7), as a result of the release of a hydrogen molecule and a C(sp3)-H bond activation on the methylene group of 3. The formation of 2, 3, 6, and 7 has been analyzed by DFT calculations. | en_US |
dc.description.sponsorship | Financial support from the MEC of Spain (Projects CTQ2005-00656, CTQ2005-9000-C02-01, and Consolider Ingenio 2010 CSD2007-00006) is gratefully acknowledged. B.E. thanks the Spanish MEC for her grant. M.B. thanks the Spanish MEC/Universidad de Zaragoza for funding through the “Ramón y Cajal” program. | en_US |
dc.format.extent | 259768 bytes | - |
dc.format.mimetype | application/pdf | - |
dc.language.iso | eng | en_US |
dc.publisher | American Chemical Society | en_US |
dc.rights | closedAccess | en_US |
dc.title | Coordination and rupture of Methyl C(sp3)−H bonds in osmium−polyhydride complexes with δ agostic interaction | en_US |
dc.type | artículo | en_US |
dc.identifier.doi | 10.1021/om700509d | - |
dc.description.peerreviewed | Peer reviewed | en_US |
dc.relation.publisherversion | http://dx.doi.org/10.1021/om700509d | en_US |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.openairetype | artículo | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.grantfulltext | none | - |
item.fulltext | No Fulltext | - |
item.languageiso639-1 | en | - |
item.cerifentitytype | Publications | - |
Aparece en las colecciones: | (ICMA) Artículos |
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