The photochemistry of W(CO)6, Mo(CO)6, and Cr(CO)6 in the presence of monomeric and polymeric triphenylphosphine ligands was investigated in toluene solution, using laser flash photolysis with 355nm excitation. The mechanism and kinetics of interaction of the primary photoproducts M(CO)5(toluene) (M = W, Mo, or Cr) with the various monomeric ligands were investigated. Interaction of the metal carbonyl photofragments with various homopolymers is also discussed. The polymerisation methods used resulted in polymers with either cyano end-groups or methyl end-groups. The nature of the end-group proved to be important in interpreting the observed reaction kinetics. The root mean square (rms) end-to-end distances of the polymer chains were also considered in rationalising the observed trends. The solution photochemistry of StyCr(CO)3, CpMn(CO)2(ri2-C8Hj4), and MeCpMn(CO)2(^-Sty)Cr(CO)3 , (Sty = Styrene; Cp = Cyclopentadienyl) was investigated in room temperature cyclohexane solution using laser flash photolysis with 355nm excitation. In StyCr(CO)3, the effect of an olefin substituent on the arene ring, on the reactivity of the photochemical intermediates produced was investigated. In the manganese complexes, olefinic ligands were directly coordinated to the metal centre, and the subsequent photochemistry was studied. The crystal and molecular structure of MeCpMn(CO)2(jU-Sty)Cr(CO)3 is also presented. This complex contains a styrene unit in an unusual bridging role between the two metal centres.