Following UV excitation, M(CO)6 (M = Cr, Mo or W) species in solution lose one CO ligand, and a solvent molecule occupies the vacant site. These photochemical reactions are studied using a transient broadband IR absorption technique with 390 fs time resolution. The progress of these reactions, including loss of the M(CO)6 reactant, appearance of a solvated M(CO)5(n-hexane) product and vibrational energy distribution and relaxation of the product, is monitored through changes in infrared absorption by the CO ligands near 2000 cm-1.