Intermediates relevant to the carbonylation of metal alkyl complexes have been generated by laser flash photolysis of the manganese acyl complexes RC(O)Mn(CO)(5) (R = CH3, CD3, CH2CH3, CH2F, CF3). This results in immediate CO photodissociation to give intermediate acyl complexes which were observed by time resolved infrared (TRIR) and time resolved optical (TRO) spectroscopy. In the presence of added ligands, such intermediates are trapped to form stable cis-substituted octahedral complexes in competition with alkyl migration from the acyl group to give the alkyl pentacarbonyl complexes RMn(CO)(5). The spectra and reactivity of the intermediate (I) derived from CH3C(O)Mn(CO)(5) (A) indicate that this exists as the chelated acyl complex (eta(2)-CH3CO)Mn(CO)(4) in weakly coordinating solvents such as cyclohexane but as the solvento species cis-CH3C(O)Mn(CO)(4)(THF) in tetrahydrofuran. Comparisons with thermal reaction kinetics support the assertion that the intermediates generated photochemically are indeed relevant to understanding the mechanism for CH3Mn(CO)(5) carbonylation. The CF3 and CH2F analogs of I are much more reactive than I in cyclohexane solution, and this has been interpreted in terms of the eta(2)-acyl configuration being destabilized by these electron-withdrawing groups. Solvent effects on the rates of methyl migration and ligand trapping reactions of the intermediate species are described and analyzed in terms of their relevance to the migratory insertion mechanism.