Stirring acetonitrile solutions of the charge-neutral pincer complexes (POCN)NiBr (1, POCN = κ^P,κ^C,κ^N-{2-(i-Pr)₂PO,6-CH₂{c-N(CH₂)₅}-C₆H₃) and (POCOP)NiBr (2, POCOP = κ^P,κ^C,κ^P′-2,6-(i-Pr₂OP)₂C₆H₃) with AgSbF₆ facilitates Br⁻ abstraction to give the corresponding cationic acetonitrile adducts [(POCN)Ni(NCMe)]⁺, 1a, and [(POCOP)Ni(NCMe)]⁺, 2a. Treating 1a and 2a with pyridine (py), 2,2′-bipyridine (bipy), phenanthroline (phen), or 4,4′-bipyridine (bipy*) gave the corresponding monocationic adducts [(POCN or POCOP)Ni(ligand)]⁺ (ligand = py: 1b and 2b; κ^N,κ^N′-bipy: 1c and 2c; κ^N,κ^N′-phen: 1d and 2d) and the dicationic dinuclear adducts [(POCN or POCOP)₂Ni₂(μ-bipy*)]²⁺ (1e and 2e). The new adducts 1a–1d and 2b–2e have been characterized by NMR spectroscopy; complex 1e proved to be insoluble and could not be analyzed by NMR. Single crystal X-ray diffraction studies were used to establish the solid-state structures of 1a–1e, and 2b–2d. UV-vis spectra have also been recorded for the pentacoordinated complexes 1c, 1d, 2c, and 2d. Studying the equilibria that govern the displacement of halides in (pincer)NiX (X = Cl, Br) by the in-coming nucleophiles py, bipy, and phen has allowed us to determine the following order for the relative nucleophilicities of the ligands involved in the halide substitution equilibria: Cl⁻ > Br⁻ > phen > bipy ≫ py > MeCN. Similar K_eq measurements showed that cationic species are better stabilized with the POCN platform compared to POCOP. This implies that POCN is a better net donor of electron density compared to POCOP, such that the relative Lewis acidity (electrophilicity) of the cationic fragments should follow the order [(POCOP)Ni]⁺ > [(POCN)Ni]⁺. Cyclic voltammetry measurements on the bipy adducts showed reversible, one-electron oxidation events occurring at a lower value for [(POCN)Ni(bipy)]⁺, implying a more electron-rich Ni(II) centre with POCN vs. POCOP. Consistent with these assertions, mixing (POCN)NiBr and [(POCOP)Ni(phen)]⁺ in acetonitrile gave [(POCN)Ni(phen)]⁺ and (POCOP)NiBr. Similarly, the K_eq value of 0.19 for the equilibrium exchange (POCN)NiCl + (POCOP)NiBr ⇆ (POCN)NiBr + (POCOP)NiCl indicates that the [(POCOP)Ni]⁺ fragment is better stabilized by Cl⁻vs. Br⁻. These exchange reactions do not occur in THF or CH₂Cl₂, implying that they are driven by the nucleophilic character of the solvent.