In the photolysis of copper(II)-chloride-alcohol-acetonitrile systems (cCu = 1 mmol l-1, copper(II)-to-chloride molar ratio 1 : 2 to 1 : 8, 10% (v/v) alcohol), Cu(II) is reduced to Cu(I), and methanol, ethanol, 1-propanol, or 1-butanol is oxidized to the corresponding aldehyde, 2-propanol to acetone. In the case of 1-propanol and 1-butanol, chlorinated aldehydes are formed in addition too. The measured quantum yields of the photoreduction of Cu(II) to Cu(I) lay in the range of ΦCu(I) = 4.5 to 40 mmol einstein-1, the absolute quantum yields of the alcohol oxidation products were 2.3 to 47 mmol einstein-1. The photoactive components are chlorocupric complexes [CuClx](2-x)+ (x = 1-4). The presence of complexes with a higher number of chloroligands in the coordination sphere (x = 3, 4) brings about a decrease in the Cu(II) photoreduction rate. The decrease in the photoreduction rate observed in the presence of dioxygen is explained in terms of re-oxidation of copper(I) by the latter, resulting in an increase in the concentration of the photochemically active cupric complexes. The catalytic aspects of the systems in question are discussed with respect to this effect.
Using internal electrostatic fields to manipulate the valence manifolds of copper complexes
