Theory of Hydride-Proton Transfer (HPT) Carbonyl Reduction by [Os III (tpy)(Cl)(NH=CHCH 3 )(NSAr)]
Journal Article
·
· Journal of the American Chemical Society
Quantum mechanical analysis reveals that carbonyl reduction of aldehydes and ketones by the imine-based reductant cis-[OsIII(tpy)(Cl)(NH=CHCH3)(NSAr)] (2), which is accessible by reduction of the analogous nitrile, occurs by hydride-proton transfer (HPT) involving both the imine and sulfilimido ligands. In carbonyl reduction, water or alcohol is necessary to significantly lower the barrier for proton shuttling between ligands. The -N(H)SAr group activates the carbonyl group through hydrogen bonding while the -NC(H)CH3 ligand delivers the hydride.
- Research Organization:
- Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
- Sponsoring Organization:
- USDOE SC Office of Basic Energy Sciences (SC-22)
- DOE Contract Number:
- SC0001011
- OSTI ID:
- 1387477
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 46 Vol. 132; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (heterogeneous)
catalysis (homogeneous)
charge transport
electrodes - solar
hydrogen and fuel cells
materials and chemistry by design
photosynthesis (natural and artificial)
solar (fuels)
solar (photovoltaic)
synthesis (novel materials)
synthesis (self-assembly)
catalysis (heterogeneous)
catalysis (homogeneous)
charge transport
electrodes - solar
hydrogen and fuel cells
materials and chemistry by design
photosynthesis (natural and artificial)
solar (fuels)
solar (photovoltaic)
synthesis (novel materials)
synthesis (self-assembly)