Heterogenized on a polystyrene anion exchange resin and in the presence of oxygen, CuCl4(2-) catalyzes the photodecomposition of chloroform at wavelengths above 345 nm with greater efficiency than an equivalent amount in homogeneous solution. The reaction is proposed to proceed in two stages, the first stage yielding CCl4 and HO2(-) as products, the second consisting of a chain reaction resulting from the CuCl4(2-)-catalyzed photodissociation of CCl4, yielding phosgene with CCl3 radicals as chain carriers. Photodecomposition is retarded by added Cl(-), CH3CN, C6H12 or C2H5OH, which is ascribed to the displacement of CHCl3 molecules from the vicinity of the copper by attraction to the polystyrene matrix or to the alkylammonium cation sites.
© 2014 The American Society of Photobiology.