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Título

2,5-norbornadiene C–C coupling reactions mediated by iridium complexes

AutorBetoré, M. Pilar; Casado, Miguel A. ; García-Orduña, P. ; Lahoz, Fernando J. ; Polo, Víctor; Oro, Luis A.
Palabras claveC–C coupling
Cross-coupling
Iridium
Fecha de publicación2016
EditorWiley-VCH
CitaciónEuropean Journal of Inorganic Chemistry 2016(21): 3489-3499 (2016)
ResumenThe treatment of [{Ir(µ-Cl)(cod)}] (cod = 1,5-cyclooctadiene) with 2,5-norbornadiene (nbd) in the presence of triethylphosphane under an atmosphere of ammonia afforded the cation complex [Ir(κC,κC-CH)(NH)(PEt)]Cl (1a) and complex [Ir(κC,κC-CH)Cl(NH)(PEt)] (1b), the structures of which include a novel seven-membered iridacycle formed by three half-coupled nbd molecules. The formation of the metallacycle has been found to occur through several steps. First, the nbd displaces the cod in [{Ir(µ-Cl)(cod)}] to give the Irchloro-bridged complex [{Ir(κC,κC-CH)(µ-Cl)(η-CH)}] (2), which bears a η-C=C-coordinated nbd and a five-membered iridacycle formed by two half-coupled nbd moieties. Further reaction with PEtinduces the C–C coupling between the iridacycle and the coordinated nbd to give the chloro-bridged complex [{Ir(κC,κC-CH)(µ-Cl)(PEt)}] (4). Finally, 4 reacts with gaseous ammonia to split the chloro bridges and form species 1a and 1b. Also, complex 2 was found to react with several donor ligands to afford the corresponding mononuclear adducts [Ir(κC,κC-CH)Cl(η-CH)(L)] [L = py (5), NH(6), PMePh (7), tBuNC (8)]. The X-ray molecular structures of 5, 7 and 8 show the presence of a five-membered iridacycle, but their stereochemistries differ by virtue of the relative locations of the respective added ligand.
URIhttp://hdl.handle.net/10261/154882
DOI10.1002/ejic.201600336
Identificadoresdoi: 10.1002/ejic.201600336
e-issn: 1099-0682
issn: 1434-1948
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