Abstract
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.
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