Recombination of Cr(CO)/sub n/ with CO: kinetics and bond dissociation energies
Journal Article
·
· J. Am. Chem. Soc.; (United States)
The pressure dependence of the recombination kinetics of Cr(CO)/sub 5/ and Cr(CO)/sub 4/ with CO has been studied with the technique of time-resolved infrared laser absorption spectroscopy. The high pressure limiting rate constants are 2.1 x 10/sup 6/ and 7.5 x 10/sup 6/ Torr/sup -1/ s/sup -1/ for Cr(CO)/sub 5/ and Cr(CO)/sub 5/, respectively. The rate at which vibrationally excited metal carbonyls, (Cr(CO)/sub n/)*, are collisionally stabilized has been estimated: k/sub s/ = 2.6 x 10/sup 5/ and 2.5 x 10/sup 7/ Torr/sup -1/ s/sup -1/ for collisions with He and Cr(CO)/sub 6/, respectively. These data, in conjunction with an RRKM model for the unimolecular decay of Cr(CO)/sub 6/ and Cr(CO)/sub 5/, allow us to determine the metal-ligand bond dissociation: energies; DH/sup 0/((CO)/sub 5/Cr-CO) = 37 +/- 5 kcal/mol and DH/sup 0/((CO)/sub 4/Cr-CO) = 25 +/- kcal/mol.
- Research Organization:
- Univ. of California, Davis (USA)
- OSTI ID:
- 7076835
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:7; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPOUNDS
DATA
DISSOCIATION ENERGY
ENERGY
EXPERIMENTAL DATA
INFORMATION
KINETICS
LASERS
MATHEMATICAL MODELS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PRESSURE DEPENDENCE
REACTION KINETICS
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHROMIUM COMPOUNDS
DATA
DISSOCIATION ENERGY
ENERGY
EXPERIMENTAL DATA
INFORMATION
KINETICS
LASERS
MATHEMATICAL MODELS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PRESSURE DEPENDENCE
REACTION KINETICS
SPECTROSCOPY
TRANSITION ELEMENT COMPOUNDS