English   español  
Please use this identifier to cite or link to this item: http://hdl.handle.net/10261/37736
Share/Impact:
Statistics
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar a otros formatos:
DC FieldValueLanguage
dc.contributor.authorPaneque, Margarita-
dc.contributor.authorMartín-Posadas, Cristina-
dc.contributor.authorLópez Poveda, Manuel-
dc.contributor.authorRendón, Nuria-
dc.contributor.authorLópez Santos, Laura-
dc.contributor.authorÁlvarez, Eleuterio-
dc.contributor.authorSalazar, Verónica-
dc.contributor.authorMereiter, Kurt-
dc.contributor.authorOñate, Enrique-
dc.date.accessioned2011-07-13T12:09:53Z-
dc.date.available2011-07-13T12:09:53Z-
dc.date.issued2007-05-27-
dc.identifier.citationOrganometallics 26(14): 3403-3415 (2007)es_ES
dc.identifier.issn0276-7333-
dc.identifier.urihttp://hdl.handle.net/10261/37736-
dc.description13 páginas, 6 figuras, 7 tablas.es_ES
dc.description.abstractThe Ir(I)−butadiene complex TpMe2Ir(η4-CH2_C(Me)C(Me)_CH2) (1) (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) reacts with ≥3 equiv of DMAD (RC CR, R = CO2Me) in CH2Cl2 at 60 °C, in the presence of adventitious water, with formation of the iridacycloheptatriene (2), by the oxidative coupling of three molecules of DMAD in the metal coordination sphere. In a related process, TpMe2IrPh2(N2) (4) gives two benzoannelated iridacycloheptatrienes, the symmetrical species (5) and the unsymmetrical one (6). The water ligand in these complexes is labile, and derivatives substituted with CO, PMe3, and NCMe have been obtained. 2, 5, and 6 react, at 25 °C, with oxo-transfer oxidizing reagents such as tBuOOH with formation of the keto-metallabicyclic products 7−9, which result from the selective oxo attack to the γ,δ-C_C double bond, irrespective of this being of the benzo or the (R)C_C(R) type. In the latter case, further oxidation takes place with tBuOOH, at ambient temperature, with formation of an iridabenzene (11) and an iridanaphthalene (12) (with five and three electron-withdrawing CO2Me substituents, respectively) in which the carboxylate MeO2CCO2- ligand completes the metal coordination sphere. Interestingly, substitution of this group by OH- or MeO- allows the formation of Jackson−Meisenheimer complexes, reflecting the inherent aromaticity of these electron-deficient metalloaromatics. Finally, the hydrogenation of the iridacycloheptatrienes has been studied. All new compounds have been fully characterized by microanalysis, IR and NMR spectroscopies, and, in some cases, single-crystal X-ray diffraction studies.es_ES
dc.description.sponsorshipFinancial support from the Spanish Ministerio de Educación y Ciencia (MEC) (projects CTQ2004-00409/BQU, FEDER support, and HU2003-039) and from the Junta de Andalucía is gratefully acknowledged. C.M.P., L.L.S., and N.R. thank the Junta de Andalucía and the MEC for research grants.es_ES
dc.language.isoenges_ES
dc.publisherAmerican Chemical Societyes_ES
dc.rightsclosedAccesses_ES
dc.subjectMetallacycloheptatrieneses_ES
dc.subjectIridiumes_ES
dc.subjectWateres_ES
dc.subjectNMR spectroscopyes_ES
dc.subjectSingle-crystal X-rayes_ES
dc.subjectIridacycloheptatrieneses_ES
dc.subjectTemperaturees_ES
dc.subjectOxidationes_ES
dc.subjectMetallaromaticses_ES
dc.titleMetallacycloheptatrienes of Iridium(III): Synthesis and Reactivityes_ES
dc.typeartículoes_ES
dc.identifier.doi10.1021/om061036o-
dc.description.peerreviewedPeer reviewedes_ES
dc.relation.publisherversionhttp://dx.doi.org/10.1021/om061036oes_ES
Appears in Collections:(IIQ) Artículos
(ICMA) Artículos
Files in This Item:
File Description SizeFormat 
accesoRestringido.pdf15,38 kBAdobe PDFThumbnail
View/Open
Show simple item record
 

Related articles:


WARNING: Items in Digital.CSIC are protected by copyright, with all rights reserved, unless otherwise indicated.