Development of Ruthenium Complexes for Water Oxidation

Abstract: Development of a methodology to combat the world energy crisis can be one of the greatest challenges now facing mankind. Our research is focused on the development of versatile catalysts (WOCs) that oxidize water into molecular oxygen at neutral pH, driven by the mild one-electron oxidant [Ru(bpy)3]3+, using natural photosynthesis a sa model.The first part of the thesis describes the unexpected generation of a mononuclear Ru complex from a hexadentate ligand, which was envisioned to accommodate two metal atoms. The study of this mononuclear catalyst clearly demonstrated the importance of having strongly electron donating functional groups and their effect on catalytic water oxidation.The second part of thesis presents the preparation of a mononuclear Ru complex, which contains two amide groups in the ligand scaffold and the superior reactivity of this complex in catalytic water oxidation under neutral condition. When mild one-electronoxidant [Ru(bpy)3]3+ was employed, TONs of ? 6000 and TOFs of ?20s-1 were achieved, which are the highest values reported so far, using this type of oxidant