Two Ni complexes are reported with κ⁴-P₂N₂ β-diimino (BDI) ligands with the general formula [Ni(XBDI)](BF₄)₂, where BDI is N-(2-(diphenylphosphaneyl)ethyl)-4-((2-(diphenylphosphaneyl)ethyl)imino)pent-2-en-2-amine and X indicates the substituent in the α-carbon intradiimine position, X = H for 1(BF₄)₂ and X = Ph for 2(BF₄)₂. Electrochemical analysis together with UV–vis and NMR spectroscopy in acetonitrile and dimethylformamide (DMF) indicates the conversion of the β-diimino complexes 1²⁺ and 2²⁺ to the negatively charged β-diketiminato (BDK) analogues (1-H)⁺ and (2-H)⁺ via deprotonation in DMF. Moreover, further electrochemical and spectroscopy evidence indicates that the one-electron-reduced derivatives 1⁺ and 2⁺ can also rapidly evolve to the BDK (1-H)⁺ and (2-H)⁺, respectively, via hydrogen gas evolution through a bimolecular homolytic pathway. Finally, both complexes are demonstrated to be active for the proton reduction reaction in DMF at E_app = −1.8 V vs Fc^+/0, being the active species the one-electron-reduced derivative 1-H and 2-H.