Photocatalytic degradation of dichloromethane by chlorocuprate(II) ions

Near UV irradiation of aerated solutions of (Et 4N) 2CuCl 4] in dichloromethane causes the decomposition of CH 2Cl 2, as evidenced by the buildup of HCl, C 2H 2Cl 4, and peroxides. A net reduction to CuCl 2] (-) occurs in the early stages, but is later reversed. In CH 2Cl 2, CuCl 4] (2-) is in equilibrium with Cu 2Cl 6] (2-), and only the latter species is photoactive. The decomposition is initiated by the photodissociation of chlorine atoms, which propagate to peroxy radicals, CHCl 2OO. Experimental evidence, including a linear dependence of the decomposition rate on the incident light intensity and on the fraction of light absorbed by Cu 2Cl 6] (2-), is consistent with a mechanism in which CHCl 2OO is reduced by electron transfer from CuCl 2] (-), following which protonation yields CHCl 2OOH. The hydroperoxide accumulates during irradiation and it too can reoxidize CuCl 2] (-). The quantum yield for HCl production at the outset of irradiation at 313 nm is 1.3 mol/einstein, based on the fraction of light absorbed by Cu 2Cl 6] (2-).