The reaction of CuCl 2 AE 2H 2 O and CdCl 2 with di-(2-picolyl)sulfide (dps) leads to the formation of mononuclear copper(II) and binuclear cadmium(II) complexes, [Cu(dps)Cl 2 ] AE H 2 O (1) and [(dps)(Cl)Cd II (l-Cl) 2 Cd II (Cl)(dps)](2). The copper atom in (1) is coordinated to one sulfur and two nitrogen atoms from the dps ligand and two chlorides in a distorted square-pyramidal environment. Complex (2) has two distorted octahedra sharing the basal edge that contain the bridging chloro ligands, each of which resides at a center of inversion. Cyclic voltammetric data show that (1) undergoes two reversible one-electron waves corresponding to Cu II /Cu III and Cu II /Cu I processes. However, cyclic voltammetry of (2) gives two irreversible reduced waves.
Two mononuclear copper(II) complexes [Cu(L)(NO 2 )](ClO 4 ) (1) and [Cu(L)(MO 4 )] 2 AE 5H 2 O (2) (L ¼ 1, 3,10, 12,16,19-hexaazatetracyclo[17,3,1,1 12.16 ,0 4.9 ]tetracosane) have been synthesized and their structures determined. Both compounds show a distorted square-pyramidal geometry with the two secondary and two tertiary amines of the macrocycle and one ligand coordinated at the axial position. Cyclic voltammetry of the complexes gives two one-electron waves corresponding to Cu II /Cu III and Cu II /Cu I processes. The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the organic ligands.
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