A Combined Experimental and Computational Study of Dihydrido-Phosphinooxazoline Iridium Complexes

Mazet, Clement; Smidt, Sebastian P.; Meuwly, Markus; Pfaltz, Andreas

doi:10.1021/ja046318z

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Title		A Combined Experimental and Computational Study of Dihydrido-Phosphinooxazoline Iridium Complexes
Authors		Mazet, Clement Smidt, Sebastian P. Meuwly, Markus Pfaltz, Andreas
Published in		Journal of the American Chemical Society. 2004, vol. 126, no. 43, p. 14176-14181
Abstract		The reaction of a [(PHOX)Ir(COD)]+ complex (COD = 1,5-cyclooctadiene) with dihydrogen was studied by NMR spectroscopy (PHOX = chiral phosphinooxazoline ligand). A single [(PHOX)Ir(H)2(COD)]+ isomer was formed as the primary product at -40 °C in THF. Subsequent reaction with H2 at -40 to 0 °C led to a mixture of two diastereomeric [(PHOX)Ir(H)2(solvent)2]+ complexes with concomitant loss of cyclooctane. The stereochemistry of the three hydride complexes could be assigned from the NMR data. The structures and energies of the observed hydride complexes and the possible stereoisomers were calculated using density functional theory. The substantial energy differences (up to 39 kcal/mol) between the various stereoisomers demonstrate the strong influence of the chiral ligand. The observed stereoselective formation of dihydride complexes can be explained by steric effects of the PHOX ligand combined with a strong electronic influence of the coordinating N and P atoms, favoring addition of a hydride trans to the Ir-N bond.
Identifiers		DOI: 10.1021/ja046318z
Full text		Article - Limited access to UNIGE
Citation (ISO format)		MAZET, Clement et al. A Combined Experimental and Computational Study of Dihydrido-Phosphinooxazoline Iridium Complexes. In: Journal of the American Chemical Society, 2004, vol. 126, n° 43, p. 14176-14181. doi: 10.1021/ja046318z https://archive-ouverte.unige.ch/unige:6991