The room temperature reaction of NiBr₂(NCCH₃)_x with the pincer-type ligand POCHOP^Ph gave the new pincer complex (POCOP^Ph)NiBr (1, POCOP^Ph = κ^P, κ^C, κ^P-2,6-{Ph₂PO}₂C₆H₃). Complex 1 reacts with AgX to give the analogous Ni–X derivatives (X = CN, 2; OSO₂CF₃, 3; OC(O)CH₃, 4; ONO₂, 5), whereas complex 3 reacts with phenylacetylene and NEt₃ to give the Ni–CCPh derivative 6. On the other hand, reaction of 1 or 3 with RLi or RMgI did not afford the desired Ni–R derivatives, giving instead the corresponding iodo and hydroxo derivatives. Complexes 1–6 have been characterized by NMR, IR, and UV-Vis spectroscopy and X-ray crystallography. The solid state structural and IR data indicate that Ni–C_sp interaction is dominated by ligand-to-metal σ-donation in 2 and 6. Cyclic voltammetry measurements indicate that complexes 3 and 4 display reversible redox behaviour (Ni^II/Ni^III); comparison of the E⁰_1/2 values for these complexes and their POCOP^i-Pr analogues shows that both the X ligands and the P-substituent have a considerable impact on the ease of oxidation in this family of complexes.