: Four new complexes of the general formula [Ni(SS)(NN)], Where SS is dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate) or pddt(6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate) and NN is bpy or phen were prepared. The UV/Vis.Spectra exhibit intense intramolecular ligand-to-ligand charge transfer bands ca.600 nm.Cyclic voltammetry shows a reversible oxidation step assigned to [Ni(SS)(NN)]0=[Ni(SS)(NN)]+ . When the complex [Ni(dddt)(bpy)] was partially oxidized by I2, a broad ESR signal at g=2.003 appeared.