Charge-transfer photochemistry of bis(diethyl-diselenocarbamato)copper(II)

The photochemical reactions of bis(diethyl-diselenocarbamato)copper(II), Cu(Et2dsc)2, complex have been studied in toluene, CH2Cl2, CHCl3 and chloroalkane/EtOH mixed solvents. Charge-transfer irradiation induces intramolecular oxidation of the ligand and reduction of copper(II) to copper(I) as evidenced by EPR and UV-Vis spectra of the complex as well as quantum yield results. When photolysis is carried out in CHCl3 or CH2Cl2 or in the solvent mixture CHCl3/EtOH resp. CH2Cl2/EtOH of lower than 1:1 EtOH content, the primary photoproduct CuI(Et2dsc) is further oxidised in a dark reaction with the chloroalkane producing the corresponding paramagnetic mixed-ligand CuII(Et2dsc)Cl complex in equilibrium with its chloride-bridged and EPR silent, dimeric form Cu2(Et2dsc)2Cl2. At low concentration of EtOH the equilibrium is shifted to the dimeric form whereas at higher than 1:1 EtOH content in the mixed solvent CHCl3/EtOH it is shifted to CuII(Et2dsc)Cl. A reaction mechanism is proposed and the role of ethanol is discussed.