Matrix photooxidation of the metal carbonyls M(CO)/sub 6/ (M = Cr, W) by the isoelectronic molecules carbon dioxide and nitrous oxide

Journal Article · Wed Jan 30 04:00:00 EST 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00197a007· OSTI ID:5738476

Almond, M J; Downs, A J; Perutz, R N

Photolysis of the hexacarbonyl molecules M(CO)/sub 6/ (M = Cr or W) in the presence of either CO/sub 2/ or N/sub 2/O has been explored by examining the IR, Raman, and UV-visible spectra of solid argon or methane matrices at ca. 20 K. Hence it has been established that the hexacarbonyl undergoes photooxidation at the hands of CO/sub 2/ or N/sub 2/O, the reaction proceeding in three stages. First, photolysis gives rise to a complex of the type XO-M(CO)/sub 5/ (X = OC or N/sub 2/), which is photochromic, being readily converted to Y-M(CO)/sub 5/ (Y = Ar, CH/sub 4/) and M(CO)/sup 6/ with the release of CO/sub 2/ or N/sub 2/O. Second, complexing activates the CO/sub 2/ or N/sub 2/O molecule to photodissociation at wavelengths far in excess of the normal thresholds, so that continued UV photolysis leads to oxidation of the metal carbonyl to oxo-metal carbonyl intermediates O/sub x/M(CO)/sub y/ containing M=O groups, e.g. trans-O/sub 2/W(CO)/sub 4/; there is simultaneous reduction of CO/sub 2/ to CO and of N/sub 2/O to N/sub 2/. In addition, Cr(CO)/sub 6/ but not W(CO)/sub 6/ gives what is believed to be a binuclear intermediate incorporating CO/sub 2/. Finally, after prolonged UV photolysis, oxidation of the metal carbonyls affords the binary metal oxide molecules CrO/sub 2/ and WO/sub 3/. 44 references, 6 figures, 3 tables.

• Research Organization: Univ. of Oxford, England
• OSTI ID: 5738476
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:3; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKANES
ARGON
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHROMIUM COMPLEXES
CHROMIUM COMPOUNDS
CHROMIUM OXIDES
COMPLEXES
DATA
DECOMPOSITION
DISSOCIATION
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
GASES
HYDROCARBONS
INFORMATION
INFRARED SPECTRA
KINETICS
LIGANDS
MATRIX ISOLATION
METHANE
NITROGEN
NITROGEN COMPOUNDS
NITROGEN OXIDES
NITROUS OXIDE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
RAMAN SPECTRA
RARE GASES
REACTION INTERMEDIATES
REACTION KINETICS
REDUCTION
REFRACTORY METAL COMPOUNDS
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPLEXES
TUNGSTEN COMPOUNDS
TUNGSTEN OXIDES
ULTRAVIOLET SPECTRA
VERY LOW TEMPERATURE