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oai:docta.ucm.es:20.500.14352/231122023-08-28T02:40:10Zcom_20.500.14352_14col_20.500.14352_15
Docta Complutense author Betoré, M. Pilar author Casado González, Miguel Ángel author García Orduña, Pilar author Lahoz, Fernando J. author Polo, Víctor author Oro, Luis A. 2023-06-18T05:42:26Z 2023-06-18T05:42:26Z 2016-07 1099-0682 10.1002/ejic.201600336 https://hdl.handle.net/20.500.14352/23112 http://onlinelibrary.wiley.com/doi/10.1002/ejic.201600336/epdf The treatment of [(Ir(μ-Cl)(cod))2] (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-C21H24)(NH3)3(PEt3)]Cl (1a) and complex [Ir(κC,κC-C21H24)Cl(NH3)2(PEt3)] (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))2] to give the IrIII chloro-bridged complex [(Ir(κC,κC-C14H16)(μ-Cl)(η4-C7H8))2] (2), which bears a η4-C=C-coordinated nbd and a five-membered iridacycle formed by two half-coupled nbd moieties. Further reaction with PEt3 induces the C-C coupling between the iridacycle and the coordinated nbd to give the chloro-bridged complex [(Ir(κC,κC-C21H24)(μ-Cl)(PEt3))2] (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-C14H16)Cl(η4-C7H8)(L)] [L = py (5), NH3 (6), PMe2Ph (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. eng 2,5-Norbornadiene C–C coupling reactions mediated by Iridium complexes journal article URL https://docta.ucm.es/bitstreams/eea7f039-b7ad-44ec-a854-a0db32b438aa/download File MD5 cad6e4ae8a783b358aab7b408c25a37a 1694791 application/pdf 2,5-Norbornadiene C–C Coupling Reactions Mediated by Iridium Complexes.pdf