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Oxidation of carbonylbis(1,2-bis(diphenylphosphino)ethane)iridium(I) cation. Activation of carbon monoxide by iridium(III) dicationic carbonyl complexes

Thesis/Dissertation ·
OSTI ID:5738831
Carbon monoxide activation has been a problem of interest to chemists for a long time. This interest stems from a desire to find feedstocks other than petroleum for use in producing chemicals and fuels. This study examines the series of complexes cis- and trans-(IrX(CO)(dppe)/sub 2/)/sup 2 +/ (X = H, Cl, Br) for activation toward nucleophilic attack at the coordinated CO. These complexes are prepared under inert atmosphere with the use of standard Schlenk-line techniques and are characterized by infrared, /sup 1/H, and /sup 31/P(/sup 1/H) NMR spectroscopies and by elemental analysis. Oxidation of Ir(CO)(dppe)/sub 2//sup +/ by halogen affords the cis iridium(III) halo isomers while oxidation by nitrosonium salts in the presence of halide affords the trans iridium(III) halo isomers. Oxidation by HCl and HBF/sub 4/ affords the trans and cis hydrido isomers, respectively. The complexes cis- and trans-(IrX(CO)(dppe)/sub 2/)/sup 2 +/ (X = H, Cl) react with nucleophiles, such as H/sub 2/O, OH/sup -/, and H/sup -/. Complexes have been isolated which are models for intermediates thought to be present in water-gas shift catalysis and in carbon monoxide hydrogenation processes. Thus, hydroxycarbonyl, formyl, and hydroxycarbene complexes have been prepared. Factors relating to the stability of these species are also discussed.
OSTI ID:
5738831
Country of Publication:
United States
Language:
English

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Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
320301 -- Energy Conservation
Consumption
& Utilization-- Industrial & Agricultural Processes-- Energy Sources
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BROMINE
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYL RADICALS
CHALCOGENIDES
CHEMICAL ACTIVATION
CHEMICAL REACTIONS
CHLORINE
COMPLEXES
DATA
ELEMENTS
EMISSION SPECTRA
EXPERIMENTAL DATA
HALOGENS
INFORMATION
INFRARED SPECTRA
IRIDIUM COMPLEXES
NMR SPECTRA
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
RADICALS
SPECTRA
TRANSITION ELEMENT COMPLEXES