RT Journal Article
T1 2,5-Norbornadiene C–C coupling reactions mediated by Iridium complexes
A1 Betoré, M. Pilar
A1 Casado González, Miguel Ángel
A1 García Orduña, Pilar
A1 Lahoz, Fernando J.
A1 Polo, Víctor
A1 Oro, Luis A.
AB 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.
PB Wiley-VCH Verlag GmbH
SN 1099-0682
YR 2016
FD 2016-07
LK https://hdl.handle.net/20.500.14352/23112
UL https://hdl.handle.net/20.500.14352/23112
LA eng
NO Ministerio de Economía y Competitividad (MINECO) /FEDER
NO Diputación General de Aragón
DS Docta Complutense
RD 6 abr 2025