Scientific article

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

Published inJournal of the American Chemical Society, vol. 126, no. 43, p. 14176-14181
Publication date2004

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.

Affiliation Not a UNIGE publication
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
Updates (1)
ISSN of the journal0002-7863

Technical informations

Creation06/18/2010 8:54:57 AM
First validation06/18/2010 8:54:57 AM
Update time03/14/2023 3:30:35 PM
Status update03/14/2023 3:30:35 PM
Last indexation10/18/2023 9:17:20 AM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack