Iridium dioxygen complexes in the oxidation of substrates: Kinetics, mechanism, and steric and electronic effects in the oxidation of CO, CO sub 2 , PPh sub 3 , and SO sub 2 by RIr(O sub 2 )(CO)L sub 2 R = Me, Ph, Np; L = PPh sub 3 , P(p-tolyl) sub 3 , PPh sub 2 Me, P(p-C sub 6 H sub 4 OMe) sub 3
- State Univ. of New York, Buffalo (USA)
The preparation, characterization, and oxygen-transfer reactivity of the iridium dioxygen complexes RIr(O{sub 2})(CO)L{sub 2} (R = Me, Ph, Np; L = PPh{sub 3}, P(p-tolyl){sub 3}, PPh{sub 2}Me, PMe{sub 2}Ph, and P(p-C{sub 6}H{sub 4}OMe){sub 3}) are reported. These complexes oxidize carbon monoxide to carbonate, sulfur dioxide to sulfate, carbon dioxide to peroxycarbonate, and triphenylphosphine to triphenylphosphine oxide but are relatively inert to other possible substrates. The kinetics of the oxidations of CO and CO{sub 2} are reported and indicate a mechanism of reversible conversion of the dioxygen from bidentate to monodentate followed by reaction with free substrate in solution. The phosphine ligand dependence on the rate of CO oxidation indicates that more electron density slightly increases the rate of oxygen transfer and that steric interactions impede the rate.
- OSTI ID:
- 6952143
- Journal Information:
- Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:16; ISSN 0002-7863; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360603* -- Materials-- Properties
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
IRIDIUM COMPOUNDS
IRIDIUM OXIDES
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
OXIDATION
OXIDES
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
SULFUR COMPOUNDS
SULFUR DIOXIDE
SULFUR OXIDES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS