Wavelength dependence of excimer laser photophysics of Cr(CO)/sub 6/ in the gas phase. A study of the infrared spectroscopy and reactions of the Cr(CO)/sub x/ (x = 5, 4, 3, 2) fragments
Journal Article
·
· J. Am. Chem. Soc.; (United States)
The transient infrared absorption spectra of the coordinatively unsaturated Cr(CO)/sub x/ species (x = 5, 4, 3, 2) that are generated via excimer laser photolysis of gas-phase Cr(CO)/sub 6/ are presented and discussed. The photofragments produced upon 193-, 248-, and 351-nm photolysis are identified. The results indicate that the gas-phase structures of the Cr(CO)/sub x/ species are the same as those observed in condensed-phase experiments. It is postulated that Cr(CO)/sub 5/ adopts a C/sub 4nu/ structure, Cr(CO)/sub 4/ adopts a C/sub 2nu/ structure, and Cr(CO)/sub 3/ adopts a C/sub 3nu/ structure. The coordinatively unsaturated species are, in general, observed to be produced with a significant amount of internal excitation. The rate constants for the reaction of Cr(CO)/sub 5/, Cr(CO)/sub 4/, and Cr(CO)/sub 3/ with CO were measured and found to be 1.5 x 10/sup 13/ cm/sup 3/ mol/sup -1/s/sup -1/, respectively.
- Research Organization:
- Northwestern Univ., Evanston, IL
- OSTI ID:
- 5390898
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 108:16; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
CARBONYLS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHROMIUM COMPLEXES
COMPLEXES
DATA
DECOMPOSITION
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
FLUIDS
GASES
INFORMATION
INFRARED SPECTRA
KINETICS
LASERS
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
REACTION KINETICS
SPECTRA
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
WAVELENGTHS
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
CARBONYLS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHROMIUM COMPLEXES
COMPLEXES
DATA
DECOMPOSITION
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
FLUIDS
GASES
INFORMATION
INFRARED SPECTRA
KINETICS
LASERS
LIGANDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
REACTION KINETICS
SPECTRA
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
WAVELENGTHS