Stoichiometric reduction of carbon monoxide in metal carbonyl complexes: the search for metal nuclearity effects
Thesis/Dissertation
·
OSTI ID:5622836
This research explores the dependence of metal cluster nuclearity on the homogeneous and heterogeneous reactions of transition metal carbonyl complexes. The effects of metal nuclearity on the proton-induced reduction of CO to CH/sub 4/ in metal carbonyls are described. A survey of the reaction of metal carbonyl complexes in neat super acid at room temperature revealed that a minimum number of 4 metals is required for the production of CH/sub 4/. Cases in which trace amounts of CH/sub 4/ were detected for 2- and 3-metal systems are thought to proceed through the initial formation of 4-metal (or larger) clusters. An important intermediate in the proton-induced reduction of CO to CH/sub 4/ in (Fe/sub 4/(CO)/sub 13/)/sup 2 -/, namely HFe/sub 4/(CH)(CO)/sub 12/, is investigated. Spectroscopic studies indicate the cluster undergoes protonation in neat HSO/sub 3/CF/sub 3/ to yield the dihydride cluster (H/sub 2/Fe/sub 4/(CH)(CO)/sub 12/)/sup +/. The reaction of HFe/sub 4/(CH)(CO)/sub 12/ with neat HSO/sub 3/CF/sub 3/ at room temperature exhibits an induction period of about 1 week, after which 1 mole of CH/sub 4/ per mole of cluster is produced over the next 50 days. Adding reducing agents to the reaction eliminates the induction period but does not significantly increase the rate of CH/sub 4/ evolution.
- OSTI ID:
- 5622836
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKANES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
GERMANIUM COMPLEXES
HYDROCARBONS
INFORMATION
IRON COMPLEXES
METHANE
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REDUCTION
TEMPERATURE DEPENDENCE
TIN COMPLEXES
TRANSITION ELEMENT COMPLEXES
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKANES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
GERMANIUM COMPLEXES
HYDROCARBONS
INFORMATION
IRON COMPLEXES
METHANE
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REDUCTION
TEMPERATURE DEPENDENCE
TIN COMPLEXES
TRANSITION ELEMENT COMPLEXES