期刊
ACS CATALYSIS
卷 4, 期 1, 页码 99-108出版社
AMER CHEMICAL SOC
DOI: 10.1021/cs400834q
关键词
transfer hydrogenation; Cp*Ir complexes; N-heterocyclic carbenes; homogeneous catalysis; kinetics; monohydride mechanism
资金
- Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001298]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences catalysis [DE-FG02-84ER13297]
- U.S. DoE [1043588]
- Alexander von Humboldt Foundation
- Yale Institute for Nanoscience and Quantum Engineering
- Centre for Sustainable Chemical Technologies at the University of Bath
- U.S. Department of Energy (DOE) [DE-FG02-84ER13297] Funding Source: U.S. Department of Energy (DOE)
Fourteen Cp*Ir-III complexes, bearing various combinations of N- and C-spectator ligands, are assayed in hydrogen-transfer catalysis from isopropyl alcohol to acetophenone under various conditions to investigate ligand effects in this widely used reaction. The new cationic complexes bearing monodentate pyridine and N-heterocyclic carbene (NHC) ligands were characterized crystallographically and by variable-temperature nuclear magnetic resonance (VT-NMR). Control experiments and mercury poisoning tests showed that iridium(0) nanoparticles, although active in the reaction, are not responsible for the high activity observed for the most active precatalyst [Cp*Ir(IMe)(2)Cl]B-4 (6). For efficient catalysis, it was found necessary to have both NHCs in monodentate form; tying them together in a bis-NHC chelate ligand gave greatly reduced activity. The kinetics of the base-assisted reaction showed induction periods as well as deactivation processes, and H/D scrambling experiments cast some doubt on the classical monohydride mechanism.
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