The increasing energy demand calls for the development of sustainable energy conversion processes. Here, the splitting of H2O to O-2 and H-2, or related fuels, constitutes an excellent example of solar-to-fuel conversion schemes. The critical component in such schemes has proven to be the catalyst responsible for mediating the four-electron oxidation of H2O to O-2. Herein, we report on the unexpected formation of a single-site Ru complex from a ligand envisioned to accommodate two metal centers. Surprising N-N bond cleavage of the designed dinuclear ligand during metal complexation resulted in a single-site Ru complex carrying a carboxylate amide motif. This ligand lowered the redox potential of the Ru complex sufficiently to permit H2O oxidation to be carried out by the mild one-electron oxidant [Ru(bpy)(3)](3+) (bpy = 2,2'-bipyridine). The work thus highlights that strongly electron-donating ligands are important elements in the design of novel, efficient H2O :oxidation catalysts.