Abstract
The transient gas-phase complexes, cis-Fe(CO)/sub 2/(C/sub 2/H/sub 4/)/sub 3/, trans-Fe(CO)/sub 2/(C/sub 2/H/sub 4/)/sub 3/, and Fe(CO)(C/sub 2/H/sub 4/)/sub 4/, are observed by time-resolved IR absorption spectrometry after pulsed laser photolysis of mixtures of Fe(CO)/sub 3/(C/sub 2/H/sub 4/)/sub 2/ and C/sub 2/H/sub 4/. The isomers of Fe(CO)/sub 2/(C/sub 2/H/sub 4/)/sub 3/ relax by two, parallel dissociate substitution pathways to reform Fe(CO)/sub 3/(C/sub 2/H/sub 4/)/sub 2/. From the CO and C/sub 2/H/sub 4/ dependencies of the observed reaction rates they obtain the 295 K unimolecular decay constants for cis-Fe-(CO)/sub 2/(C/sub 2/H/sub 4/)/sub 3/ and trans-Fe(CO)/sub 2/(C/sub 2/H/sub 4/)/sub 3/, 3.6 +/- 0.9 x 10/sup 3/ and 1.2 +/- 0.4 x 10/sup 3/ s/sup -1/, respectively. The ratios of the bimolecular rate constants for CO and C/sub 2/H/sub 4/ recombination with the coordinatively unsaturated species, Fe(CO)/sub 2/(C/sub 2/H/sub 4/)/sub 2/, are found to be approx. 400, favoring reaction with CO.
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