The four-electron oxidation of water (2H2O → O2 + 4H+ + 4e−) is considered the main bottleneck in artificial photosynthesis. In nature, this reaction is catalysed by a Mn4CaO5 cluster embedded in the oxygen-evolving complex of photosystem II. Ruthenium-based complexes have been successful artificial molecular catalysts for mimicking this reaction. However, for practical and large-scale applications in the future, molecular catalysts that contain earth-abundant first-row transition metal ions are preferred owing to their high natural abundance, low risk of depletion, and low costs. In this review, the frontier of water oxidation reactions mediated by first-row transition metal complexes is described. Special attention is paid towards the design of molecular structures of the catalysts and their reaction mechanisms, and these factors are expected to serve as guiding principles for creating efficient and robust molecular catalysts for water oxidation using ubiquitous elements.
