Molecular organoosmium chemistry and catalysis on the basic magnesium oxide surface

Journal Article · Wed Jan 08 04:00:00 EST 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00261a014· OSTI ID:6036763

Lamb, H H; Gates, B C

The complex (H/sub 2/Os(CO)/sub 4/) is deprotonated upon adsorption on the basic surface of magnesia. The resulting (HOs(CO)/sub 4/)/sup -/ is held strongly to the surface by a localized carbonyl-Mg/sup 2 +/ interaction analogous to the contact anion ion pairing observed for (Na)(HOs(CO)/sub 4/) in THF. The surface-bound complex is the precursor of surface species that are catalytically active for CO hydrogenation to give methane and higher hydrocarbons at 275 /sup 0/C and 10 atm. During catalysis, the mononuclear anion is transformed into the stable (H/sub 3/Os/sub 4/(CO)/sub 12/)/sup -/ and (Os/sub 10/C(CO)/sub 24/)/sup 2 -/, which become the only surface species detected by infrared spectroscopy and by extraction of surface-bound anions. The chemistry of the molecular condensation reactions of osmium carbonyls on the basic magnesia surface closely parallels that of osmium carbonyls in basic solution. The tetranuclear osmium cluster is suggested to be involved in the CO hydrogenation catalysis. 51 references, 12 figures, 1 table.

• Research Organization: Univ. of Delaware, Newark
• OSTI ID: 6036763
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:1; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ADSORPTION
ALKALINE EARTH METAL COMPOUNDS
ANIONS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHARGED PARTICLES
CHEMICAL REACTIONS
COMPLEXES
DATA
EXPERIMENTAL DATA
HIGH TEMPERATURE
INFORMATION
INFRARED SPECTRA
IONS
MAGNESIUM COMPOUNDS
MAGNESIUM OXIDES
METHANATION
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OSMIUM COMPLEXES
OXIDES
OXYGEN COMPOUNDS
PH VALUE
SORPTION
SPECTRA
SURFACE PROPERTIES
TRANSITION ELEMENT COMPLEXES