A Combined Experimental and Computational Study of Dihydrido(phosphinooxazoline)iridium Complexes
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...
Saved in:
Published in | Journal of the American Chemical Society Vol. 126; no. 43; pp. 14176 - 14181 |
---|---|
Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Washington, DC
American Chemical Society
03.11.2004
|
Subjects | |
Online Access | Get full text |
Cover
Loading…
Summary: | 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. |
---|---|
Bibliography: | istex:D63326DA16B029794B41E617E85741A68C465E2E ark:/67375/TPS-05TR5TCH-D ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0002-7863 1520-5126 |
DOI: | 10.1021/ja046318z |