Time-resolved spectroscopic techniques have been used to prepare and to interrogate transient species that are models for reactive intermediates in cobalt-catalyzed hydroformylation. Flash photolysis of acetylcobalt carbonyl complexes of the type RC(O)Co(CO)(3)(PR'(3)) (A; R = CH3, CD3, or C2H5; R' = Ph or Bu-n) leads to CO photodissociation to give the "unsaturated" intermediate [RC(O)CO(CO)(2)(PR'(3))] (1), which decays by two competitive pathways, alkyl migration to the cobalt to give RCo(CO)(3)PR'(3) (M) and reaction with CO to re-form A. With the perdeuterioacetyl complex (R = CD3, R' = Ph), rate constants both of CO trapping (k(CO)) and of methyl migration (km) were just slightly smaller than those of the perprotio analogue (k(h)/k(d) = 1.04 +/- 0.01 and 1.07 +/-0.09, respectively). Thus, any stabilization of the "vacant" coordination site of 1 by agostic interactions with the acetyl methyl group appears to be kinetically insignificant, consistent with the previous conclusion (Inorg. Chem. 2000, 39, 3098-3106) that this site is stabilized by an eta(2)-Coordinated carbonyl. Changing the phosphine ligand has a greater influence on the kinetics of 1. The species generated by the flash photolysis of the trialkyl phosphine complex CH3C(O)CO-(CO)(3) (P(Bu-n(3))) exhibited a much larger km than was the case for the PPh3 analogue, although there was little difference in the k(CO) values. Similarly, km proved to be sensitive to the nature of R as demonstrated by the slower alkyl migration (at 298 K) for the intermediate formed by CO photodissociation from the propionyl complex C2H5C(O)CO(CO)(3)PPh3 relative to the acetyl analogue. Nonetheless, all these intermediates displayed analogous time-resolved infrared spectra and general kinetics behavior in benzene solution (implying common mechanisms for decay), so it is concluded that all are present as the eta(2)-chelated acyl structure under these conditions.