Abstract
Laser-based time-resolved infrared absorption spectroscopy has been applied to the study of the 248-nm photolysis of the pseudo-nickel carbonyl, tricarbonylnitrosylcobalt, in the gas phase. Co(CO)/sub 3/NO dissociates by a series of sequential ligand eliminations to give predominantly CoCO. This species reacts back with parent Co(CO)/sub 3/NO with a gas kinetic rate constant of (6.4 +/- 0.6) x 10/sup -10/ cm/sup 3/ molecule/sup -1/ s/sup -1/ to form a binuclear species, (Co/sub 2/(CO)/sub 4/NO), of unknown structure. Added CO results in the formation of Co(CO)/sub 3/ and finally Co(CO)/sub 4/. The rate constant for the reactions of CO with Co(CO) is (6.2 +/- 0.6) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ which is also a lower limit for the rates of reaction of CO with Co(CO)/sub 2/ and Co(CO)/sub 3/. This behavior shows marked similarity with recent work on the other carbonyls and begins to establish a general pattern for metal carbonyl photolysis.
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