Hydrogen tunneling in the activation of dioxygen by a tris(pyrazolyl)borate cobalt complex
Journal Article
·
· Journal of the American Chemical Society; (United States)
- Univ. of Delaware, Newark, DE (United States)
The activation of dioxygen by coordination to metals plays an important role in living organisms as well as artificial oxidation catalysts. We have previously described the dioxygen complex Tp[prime]Co[sup II](O[sub 2]) (Tp[prime] = hydridotris (3-tert-butyl-5-methylpyrazolyl)borate) and its reaction with Tp[prime]Co[sup I](N[sub 2]) to yield Tp[prime]Co[sup II]OH, the apparent product of hydrogen atom abstraction by a highly reactive cobalt - oxo complex. Herein we report related chemistry of the Tp[double prime]Co-moiety (Tp[double prime] = hydridotris (3-isopropyl-5-methylpyrazolyl) borate), including the observation of an intermediate and evidence for a tunneling contribution to hydrogen atom abstraction from the ligand. 16 refs., 1 fig.
- DOE Contract Number:
- FG02-92ER14273
- OSTI ID:
- 6954414
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:15; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Wed May 11 00:00:00 EDT 1994
· Inorganic Chemistry
·
OSTI ID:450861
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
661300 -- Other Aspects of Physical Science-- (1992-)
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
CHEMICAL ACTIVATION
CHEMICAL BONDS
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
DECOMPOSITION
DEUTERIUM COMPOUNDS
ELEMENTS
ENTHALPY
ENTROPY
HYDROGEN
HYDROGEN COMPOUNDS
LIGANDS
MAGNETIC RESONANCE
NONMETALS
NUCLEAR MAGNETIC RESONANCE
OXYGEN
PHYSICAL PROPERTIES
RESONANCE
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES
TUNNEL EFFECT
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
661300 -- Other Aspects of Physical Science-- (1992-)
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
CHEMICAL ACTIVATION
CHEMICAL BONDS
CHEMICAL REACTIONS
COBALT COMPLEXES
COMPLEXES
DECOMPOSITION
DEUTERIUM COMPOUNDS
ELEMENTS
ENTHALPY
ENTROPY
HYDROGEN
HYDROGEN COMPOUNDS
LIGANDS
MAGNETIC RESONANCE
NONMETALS
NUCLEAR MAGNETIC RESONANCE
OXYGEN
PHYSICAL PROPERTIES
RESONANCE
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES
TUNNEL EFFECT