Por favor, use este identificador para citar o enlazar a este item:
http://hdl.handle.net/10261/159054
COMPARTIR / EXPORTAR:
SHARE CORE BASE | |
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE | |
Campo DC | Valor | Lengua/Idioma |
---|---|---|
dc.contributor.author | Zamorano, Ana | es_ES |
dc.contributor.author | Rendón, Nuria | es_ES |
dc.contributor.author | López-Serrano, Joaquín | es_ES |
dc.contributor.author | Álvarez, Eleuterio | es_ES |
dc.contributor.author | Carmona, Ernesto | es_ES |
dc.date.accessioned | 2018-01-15T08:10:52Z | - |
dc.date.available | 2018-01-15T08:10:52Z | - |
dc.date.issued | 2018 | - |
dc.identifier.citation | Inorganic Chemistry, 57 (1), pp 150–162 (2018) | es_ES |
dc.identifier.uri | http://hdl.handle.net/10261/159054 | - |
dc.description.abstract | We report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(η5-C5Me5)M(N^N)]+ (3-M+), where N^N represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)C5H3N (Xyl = 2,6-Me2C6H3). The two complexes were isolated as salts of the BArF anion (BArF = B[3,5-(CF3)2C6H3]4). The M–Namido bond of complexes 3-M+ readily activated CO, C2H4, and H2. Thus, compounds 3-M+ reacted with CO under ambient conditions, but whereas for 3-Rh+, CO migratory insertion was fast, yielding a carbamoyl carbonyl species, 4-Rh+, the stronger Ir–Namido bond of complex 3-Ir+ caused the reaction to stop at the CO coordination stage. In contrast, 3-Ir+ reacted reversibly with C2H4, forming adduct 5-Ir+, which subsequently rearranged irreversibly to [Ir](H)(═C(Me)N(Ph)−) complex 6-Ir+, which contains an N-stabilized carbene ligand. Computational studies supported a migratory insertion mechanism, giving first a β-stabilized linear alkyl unit, [Ir]CH2CH2N(Ph)–, followed by a multistep rearrangement that led to the final product 6-Ir+. Both β- and α-H eliminations, as well as their microscopic reverse migratory insertion reactions, were implicated in the alkyl-to-hydride–carbene reorganization. The analogous reaction of 3-Rh+ with C2H4 originated a complex mixture of products from which only a branched alkyl [Rh]C(H)(Me)N(Ph)– (5-Rh+) could be isolated, featuring a β-agostic methyl interaction. Reactions of 3-M+ with H2 promoted a catalytic isomerization of the Ap ligand from classical κ2-N,N′ binding to κ-N plus η3-pseudoallyl coordination mode. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.relation.isversionof | Postprint | es_ES |
dc.rights | openAccess | en_EN |
dc.title | Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (5-C5Me5)M-Aminopyridinate Complexes | es_ES |
dc.type | artículo | es_ES |
dc.identifier.doi | 10.1021/acs.inorgchem.7b02283 | - |
dc.description.peerreviewed | Peer reviewed | es_ES |
dc.relation.publisherversion | htpp://dx.doi.org/10.1021/acs.inorgchem.7b02283 | es_ES |
dc.embargo.terms | 2018-12-18 | es_ES |
dc.relation.csic | Sí | es_ES |
oprm.item.hasRevision | no ko 0 false | * |
dc.type.coar | http://purl.org/coar/resource_type/c_6501 | es_ES |
item.openairetype | artículo | - |
item.grantfulltext | open | - |
item.cerifentitytype | Publications | - |
item.openairecristype | http://purl.org/coar/resource_type/c_18cf | - |
item.fulltext | With Fulltext | - |
item.languageiso639-1 | en | - |
Aparece en las colecciones: | (IIQ) Artículos |
Ficheros en este ítem:
Fichero | Descripción | Tamaño | Formato | |
---|---|---|---|---|
2018 Inorg Chem Nuria Rendon COMPLETO.pdf | 8,38 MB | Adobe PDF | Visualizar/Abrir |
CORE Recommender
SCOPUSTM
Citations
13
checked on 13-abr-2024
WEB OF SCIENCETM
Citations
12
checked on 25-feb-2024
Page view(s)
277
checked on 23-abr-2024
Download(s)
335
checked on 23-abr-2024
Google ScholarTM
Check
Altmetric
Altmetric
NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.