Superoxide dismutases (SOD) are unique metalloenzymes that catalyzes the dismutation of superxoide into hydrogen peroxide and oxygen. Recently a new class of SOD was isolated which contains nickel at the active site (NiSOD). It was discovered that within its reduced form NiSOD has a square planar coordination environment around the metal center, including two two cis-cysteinate sulfurs and two nitrogens, one from an amide and the other from the N-terminal amine. While oxidized, the Ni(III) will have a fifth coordination bond coming from an axial imidazol nitrogen. In order to understand the stability and mechanism of this natural N2S2 coordination mode of NiSOD, we have prepared a series of new ligands imitating the coordination environment of the active site in NiSOD. While all these ligand have N2S2 coordination sites, the nitrogen donors can come from either two amides, or two amines, or the amide/amine style. Small molecule nickel complexes were also synthesized with these new ligands. Crystal structures, electrochemistry as well as some spectroscopic data of these metal complexes are also reported here.