The design of hydrogen-evolving electrocatalysts that operate at modest overpotentials is important for solar energy devices. The M-II/I reduction potential for metal diimine-dioxime and diglyoxime electrocatalysts is often related to the overpotential required for hydrogen evolution. Herein the impact of ligand modification and protonation on the M-II/I reduction potentials for cobalt, nickel, and iron diimine-dioxime and diglyoxime complexes is investigated with computational methods. The calculations are consistent with experimental data available for some of these complexes and additionally provide predictions for complexes that have not yet been synthesized. The calculated pK(a)'s imply that ligand protonation is likely to occur at the O-H-O bridge but not at other ligand sites for these complexes. Moreover, the calculations imply that a ligand-protonated Cow-hydride intermediate is formed along the H-2 production pathway for catalysts containing an O-H-O bridge in the presence of sufficiently strong acid. The calculated M-II/I reduction potentials indicate that the anodic shift due to protonation of the O-H-O bridge is greater than that due to replacing the O-H-O bridge with an O-BF2-O bridge for cobalt and nickel but not for iron complexes. Experiments suggest degradation for complexes with two O-H-O bridges and alternative mechanisms for certain iron complexes with two O-BF2-O bridges. Asymmetric cobalt, nickel, and strongly electron withdrawing substituted iron diimine-dioxime and diglyoxime complexes containing a single O-H-O bridge are proposed to be effective hydrogen evolution electrocatalysts with relatively low overpotentials in acetonitrile and water. These insights are important for the design of efficient aqueous-based hydrogen-evolving catalysts.