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Título: | C–N bond coupling reactions of ammonia with acetone promoted by iridium and rhodium complexes: Experimental and DFT studies |
Autor: | Betoré, M. Pilar CSIC; García-Orduña, Pilar CSIC ORCID; Lahoz, Fernando J. CSIC ORCID; Casado, Miguel A. CSIC ORCID; Polo, Víctor CSIC ORCID; Oro, Luis A. CSIC ORCID | Palabras clave: | C-C coupling C-N coupling Ammonia Rhodium Iridium |
Fecha de publicación: | 2016 | Editor: | Wiley-VCH | Citación: | European Journal of Inorganic Chemistry 2016(34): 5347-5355 (2016) | Resumen: | Treatment of acetone solutions of the known chlorido-bridged complexes [{M(µ-Cl)(cod)}2] (M = Ir, Rh; cod = 1,5-cyclooctadiene) under an ammonia atmosphere afforded the cationic complexes {M(cod)[κN,κN-NH2–C(CH3)2–CH2–C(CH3)=NH]}Cl [M = Ir (3), Rh (4)]. The molecular structures of 3 and 4 showed the formation of six-membered metallacycles due to the presence of a 4-imino-2-methylpentan-2-amine-κN,κN-chelated ligand. Alternatively, the cations [M(cod)(NCCH3)2]BF4 (M = Ir, Rh) reacted with gaseous ammonia at atmospheric pressure affording bis(ammine) complexes [M(cod)(NH3)2]BF4 [M = Ir (5), Rh (6)], which were found to react with acetone, forming cations [M(cod)(κN,κN-NH2–C(CH3)2–CH2–C(CH3)=NH)]BF4 [M = Ir (7), Rh (8)]. DFT studies reveal that the transformation of 6 into 8 is mediated by NH3 molecules acting as an external base. The reaction is triggered by deprotonation of an ammonia ligand forming a amido–metal intermediate, which further transforms into an acetimino ligand through aldol condensation. The terminal methyl group of one acetimino ligand is deprotonated by NH3 yielding an enamine ligand, which can react with the imine ligand through concerted nucleophilic addition to afford the metallacycle, which is stabilized by protonation. | URI: | http://hdl.handle.net/10261/154801 | DOI: | 10.1002/ejic.201600925 | Identificadores: | doi: 10.1002/ejic.201600925 e-issn: 1099-0682 issn: 1434-1948 |
Aparece en las colecciones: | (ISQCH) Artículos |
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