In electrochemical oxidations, the second oxidation potential of phenylenediamines (PD) varies because of hydrogen-bonding formation for PD(+•) with pyridines. A linear relationship was obtained for the potential shift as a function of pK(a) of the protonated pyridines and potential inversion could be observed. The oxidized PD(+•) could also form hydrogen bonding with alcohols and the shift of potential exhibits a different pattern.

The utilization of earth‐abundant low‐toxicity metal ions in the construction of highly active and efficient molecular catalysts promoting the water oxidation reaction is important for developing a sustainable artificial energy cycle. However, the kinetic and thermodynamic properties of the currently available molecular water oxidation catalysts (MWOCs) have not been comprehensively investigated. This Review summarizes the current status of MWOCs based on first‐row transition metals in terms of their turnover frequency (TOF, a kinetic property) and overpotential (η, a thermodynamic property) and uses the relationship between log(TOF) and η to assess catalytic performance. Furthermore, the effects of the same ligand classes on these MWOCs are discussed in terms of TOF and η, and vice versa. The collective analysis of these relationships provides a metric for the direct comparison of catalyst systems and identifying factors crucial for catalyst design.

In this study, dinuclear cobalt complexes (1 and 2) featuring bis(benzimidazole)pyrazolide-type ligands (H 2 L and Me 2 L) were prepared and evaluated as molecular electrocatalysts for water oxidation. Notably, 1 bearing a non-innocent ligand (H 2 L) displayed faster catalytic turnover than 2 under alkaline conditions, and the base dependence of water oxidation and kinetic isotope effect analysis indicated that the reaction mediated by 1 proceeded by a different mechanism relative to 2. Spectroelectrochemical, cold-spray ionization mass spectrometric and computational studies found that double deproto-nation of 1 under alkaline conditions cathodically shifted the catalysis-initiating potential and further altered the turnoverlimiting step from nucleophilic water attack on (H 2 L)Co III 2 (superoxo) to deprotonation of (L)Co III 2 (OH) 2 . The rateoverpotential analysis and catalytic Tafel plots showed that 1 exhibited a significantly higher rate than previously reported Ru-based dinuclear electrocatalysts at similar overpotentials. These observations suggest that using non-innocent ligands is a valuable strategy for designing effective metal-based molecular water oxidation catalysts.