dc.creator | Zamorano Márquez, Ana | es |
dc.creator | Rendón Márquez, Nuria | es |
dc.creator | López Serrano, Joaquín | es |
dc.creator | Álvarez González, Eleuterio | es |
dc.creator | Carmona Guzmán, Ernesto | es |
dc.date.accessioned | 2019-07-05T15:16:46Z | |
dc.date.available | 2019-07-05T15:16:46Z | |
dc.date.issued | 2018 | |
dc.identifier.citation | Zamorano Márquez, A., Rendón Márquez, N., López Serrano, J., Álvarez González, E. y Carmona Guzmán, E. (2018). Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes. Inorganic Chemistry, 57 (1), 150-162. | |
dc.identifier.issn | 0020-1669 | es |
dc.identifier.issn | 1520-510X | es |
dc.identifier.uri | https://hdl.handle.net/11441/87894 | |
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 |
dc.description.sponsorship | Ministerio de Economía y Competitividad CTQ2016-80814-R, CTQ2016-75193-P, CTQ2016-81797-REDC | es |
dc.description.sponsorship | Junta de Andalucía FQM-119 | es |
dc.format | application/pdf | es |
dc.language.iso | eng | es |
dc.publisher | American Chemical Society | es |
dc.relation.ispartof | Inorganic Chemistry, 57 (1), 150-162. | |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.title | Activation of Small Molecules by the Metal-Amido Bond of Rhodium(III) and Iridium(III) (η5-C5Me5)M-Aminopyridinate Complexes | es |
dc.type | info:eu-repo/semantics/article | es |
dc.type.version | info:eu-repo/semantics/submittedVersion | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.contributor.affiliation | Universidad de Sevilla. Departamento de Química Inorgánica | es |
dc.relation.projectID | CTQ2016-80814-R | es |
dc.relation.projectID | CTQ2016-75193-P | es |
dc.relation.projectID | CTQ2016-81797-REDC | es |
dc.relation.projectID | FQM-119 | es |
dc.relation.publisherversion | http://dx.doi.org/10.1021/acs.inorgchem.7b02283 | es |
dc.identifier.doi | 10.1021/acs.inorgchem.7b02283 | es |
idus.format.extent | 87 p. | es |
dc.journaltitle | Inorganic Chemistry | es |
dc.publication.volumen | 57 | es |
dc.publication.issue | 1 | es |
dc.publication.initialPage | 150 | es |
dc.publication.endPage | 162 | es |