Iridicycle-Catalysed Imine Reduction: An Experimental and Computational Study of the Mechanism

• Published in: Chemistry : a European journal Vol. 21; no. 46; pp. 16564 - 16577
• Main Authors: Chen, Hsin-Yi Tiffany, Wang, Chao, Wu, Xiaofeng, Jiang, Xue, Catlow, C. Richard A., Xiao, Jianliang
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 09.11.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Catalysts; Chemistry; Chemistry, Multidisciplinary; Computer applications; density functional calculations; Density functional theory; Formates; Formations; Formic acid; homogeneous catalysis; Hydrides; Imines; Ion pairs; iridium; Kinetics; Magnetic resonance spectroscopy; Methanol; Methyl alcohol; NMR; NMR spectroscopy; Nuclear magnetic resonance; Physical Sciences; Reaction kinetics; Reduction; Science & Technology; transfer hydrogenation; Vapor phases; LIGAND BIFUNCTIONAL CATALYSIS; ASYMMETRIC TRANSFER HYDROGENATION; EFFECTIVE CORE POTENTIALS; imines; transfer hydrogenation; CARBON-DIOXIDE HYDROGENATION; ELASTIC BAND METHOD; DENSITY-FUNCTIONAL THERMOCHEMISTRY; AB-INITIO PSEUDOPOTENTIALS; iridium; density functional calculations; CYCLOMETALATED IRIDIUM COMPLEXES; homogeneous catalysis; HYDROXYCYCLOPENTADIENYL RUTHENIUM HYDRIDE; FORMIC-ACID DEHYDROGENATION

The mechanism of imine reduction by formic acid with a single‐site iridicycle catalyst has been investigated by density functional theory (DFT), NMR spectroscopy, and kinetic measurements. The NMR and kinetic studies suggest that the transfer hydrogenation is turnover‐limited by the hydride formatio...