Fourier transform infrared studies of atomic Ti, V, Cr, Fe, Co, Ni, and Cu reactions with carbon dioxide in low-temperature matrices
Titanium, vanadium, chromium, iron, cobalt, nickel, and copper metal atoms were cocondensed with CO/sub 2/ in neat matrices at 15 K. Even though a large proportion of atoms do not react, new complexes with CO/sub 2/ are characterized by using FTIR techniques and their infrared absorption bands are assigned. It is clearly shown that CO/sub 2/ is highly bent in these complexes. The behavior of oxophile metals is different from that of other metals which spontaneously form 1:1 complexes with CO/sub 2/. For Ti, V, and Cr, the authors observe first an insertion of metallic atom into a CO bond, leading to the formation of the intermediate (O)M(CO) molecule, followed by the CO/sub 2/ fixation on this complex, to form (O)M(CO)(CO/sub 2/). The other identified products in the matrices are CO, M(O), M(CO)/sub n/, and possibly a few carbonates. Most complexes are thermally unstable and decompose above 60 K. Only Fe and Ni compounds give rise upon annealing above 80 K to CO/sub 2/ reduction to CO along with the simultaneous formation of metal carbonyl complexes. Isotopic experiments with /sup 13/CO/sub 2/ and C/sup 18/O/sub 2/ allow them to conclude that the geometry of complexes is both metal and matrix dependent: in neat CO/sub 2/ matrices, Fe and CO lead to a C coordination, the others being fixed in a side-on and end-on manner.
- Research Organization:
- Universite de Bordeaux I, Talence (France)
- OSTI ID:
- 7005290
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 92:8
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
54 ENVIRONMENTAL SCIENCES
CARBON DIOXIDE
CHEMICAL REACTIONS
CHROMIUM
COBALT
COPPER
IRON
NICKEL
TITANIUM
VANADIUM
ABSORPTION SPECTROSCOPY
CARBON 13
COMPLEXES
EXPERIMENTAL DATA
FOURIER TRANSFORM SPECTROMETERS
INFRARED SPECTRA
LOW TEMPERATURE
MATRIX ISOLATION
OXYGEN 18
STRUCTURAL CHEMICAL ANALYSIS
VERY LOW TEMPERATURE
CARBON COMPOUNDS
CARBON ISOTOPES
CARBON OXIDES
CHALCOGENIDES
DATA
ELEMENTS
EVEN-EVEN NUCLEI
EVEN-ODD NUCLEI
INFORMATION
ISOTOPES
LIGHT NUCLEI
MEASURING INSTRUMENTS
METALS
NUCLEI
NUMERICAL DATA
OXIDES
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
SPECTRA
SPECTROMETERS
SPECTROSCOPY
STABLE ISOTOPES
TRANSITION ELEMENTS
400201* - Chemical & Physicochemical Properties
500100 - Environment
Atmospheric- Basic Studies- (-1989)