Synthesis and characterization of divalent nickel complexed by 2-pyridylpyrrolide bidentate ligands are reported, as possible precursors to complexes with redox active ligands. Varied substituents on the pyrrolide, two CF3 (L-2), two Bu-t (L-0), and one of each type (L-1) are employed and the resulting Ni(L-n)(2) complexes show different Lewis acidity toward CO, H2O, tetrahydrofuran (THF), or MeCN, the L-2 case being the most acidic. Density functional theory calculations show that the frontier orbitals of all three Ni(L-n)(2) species are localized at the pyrrolide groups of both ligands and Ni(L-n)(2)(+) can be detected by mass spectrometry and in cyclic voltammograms (CVs). Following cyclic voltammetry studies, which show electroactivity primarily in the oxidative direction, reactions with pyridine N-oxide or Br-2 are reported. The former yield simple bis adducts, Ni(L-2)(2)(pyNO)(2) and the latter effects electrophilic aromatic substitution of the one pyrrolide ring hydrogen for both chelates, leaving it brominated.