The photochemistry of MeCpMn(CO)3 dispersed in polymer films at low temperatures was investigated using infrared or UV/visible detection. The photolysis of the isoelectronic ArCr(CO)3 complex in low temperature polymer films was then studied for comparison purposes and because the parent tricarbonyl bands were obscuring some of the bands arising from the photoproducts in the manganese system. As the higher energy infrared bands arising from the photoproducts in both tricarbonyl systems were masked the photochemistry of Cr(CO)e dispersed in polystyrene at low temperatures was examined. The solution photochemistry of the MeCpMn(CO)3 and ArCr(CO)3 complexes in ambient temperature toluene was investigated by laser flash photolysis, 355 nm excitation, with UV/vis detection. The mechanism and kinetics of the reaction of the primary photoproducts with both monomeric and polymeric pyridine ligands was then examined. As different trends were observed for the manganese and chromium tricarbonyl systems, the interaction of the Cr(CO)5 (toluene) fragment with the various pyridine ligands was investigated. A polymer-anchored chromium tricarbonyl complex was prepared and its photochemistry was studied by laser flash photolysis. The kinetics of the reaction of the polymer-bound primary photoproduct with pyridine ligands was then examined.