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Recombination of Cr(CO)/sub n/ with CO: kinetics and bond dissociation energies

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00215a014· OSTI ID:7076835
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