The reaction between Cp(PPh 3 ) 2 Ru-CN and CuCl 2 results in Cp(PPh 3 ) 2 Ru-CN-CuCl (1) as the main product and Cl(CH 3 CN)(PPh 3 )Ru{CN-CuCl}{NC-Ru(PPh 3 ) 2 Cp} 2 (2) as the side product. cis-(bpy) 2 Fe(CN) 2 reacts with both CuCl 2 and CuCl to form [(bpy) 2 Fe(CN)(CN-CuCl 2 )] x (3) and [(bpy) 2 Fe(CN)(CN-CuCl)] x (4). Upon attempts at recrystallization the former partly decomposes with formation of (bpy) 2 Fe{CN-CuCl 2 (bpy)} 2 (5). Electrochemical data of the complexes are reported. Complexes 1, 2, and 5 were identified by structure determinations.