Abstract The photochemical oxidation of CpW (CO) 3 Cl (Cp= η 5-C 6 H 5) by carbon tetrachloride and other polychlorocarbons affords CpW (CO) 2 Cl 3. The sole photoprocess is dissociation of CO from the complex to give CpW (CO) 2 Cl. The major pathway of the oxidation involves the net transfer of two halogen atoms from one halocarbon molecule to the unsaturated metal complex. Pathways involving the formation of trichloromethyl radical ...