The preparation of complexes trans-[Ni(-SeC6H4-o-NH-)(2)](-) (1), cis-[Ni(-TeC6H4-o-NH-)(2)](-) (2), trans-[Ni(-SC6H4-o-NH-)2](-) (3), and [Ni(-SC6H4-o-S-)(2)]- (4) by oxidative addition of 2-aminophenyl dichalcogenides to anionic [Ni(CO)(SePh)(3)](-) proves to be a successful approach in this direction. The cis arrangement of the two tellurium atoms in complex 2 is attributed to the intramolecular (TeTe)-Te-... contact interaction ((TeTe)-Te-... contact distance of 3.455 Angstrom). The UV-vis electronic spectra of complexes 1 and 2 exhibit an intense absorption at 936 and 942 nm, respectively, with extinction coefficient epsilon > 10000 L mol(-1) cm(-1). The observed small g anisotropy, the principal g values at g(1) = 2.036, g(2) = 2.062, and g(3) = 2.120 for 1 and g(1) = 2.021, g(2) = 2.119, and g(3) = 2.250 for 2, respectively, indicates the ligand radical character accompanied by the contribution of the singly occupied d orbital of Ni(III). The X-ray absorption spectra of all four complexes show L-III peaks at similar to854.5 and similar to853.5 eV. This may indicate a variation of contribution of the Ni(II)-Ni(III) valence state. According to the DFT calculation, the unpaired electron of complex 1 and 2 is mainly distributed on the 3d(xz) orbital of the nickel ion and on the 4p(z) orbital of kselenium (tellurium, 5p(z)) as well as the 2p(z) orbital of nitrogen of the ligand. On the basis of X-ray structural data, UV-vis absorption, electron spin resonance, magnetic properties, DFT computation, and X-ray absorption (K- and L-edge) spectroscopy, the monoanionic trans-[Ni(-SeC6H4-o-NH-)(2)](-) and cis-[Ni(-TeC6H4-o-NH-)(2)](-) complexes are appositely described as a resonance hybrid form of Ni(III)-bis(o-amidochalcogenophenolato(2-)) and Ni(II)-(o-amidochalcogenophenolato(2-))-(o-iminochalcogenobenzosemiquinonato(1-) pi-radical; i.e., complexes 1 and 2 contain delocalized oxidation levels of the nickel ion and ligands.