Nature has provided us with a guide for converting water, carbon dioxide, and sunlight into useful chemical fuels. The oxidation of water represents a critical medium for generating the protons and electrons necessary to produce such fuels (e.g., hydrogen, methane, methanol). Molecular catalysts capable of mediating water oxidation provide mechanistic insights that can ultimately be used to design highly active materials that can scale to meet global demand. The recent recognition that relatively simple molecules can mediate the demanding thermodynamic and kinetic requirements of water oxidation has proven to be a huge advance for the field. One such molecule, [RuII(tpy)(bpy)(OH2)]2+, represents an archetypal molecular scaffold that can be readily modified to gain a better understanding of how electronic and steric factors contribute to catalyst stability and activity. The outcome of these studies helped guide our pursuit of catalysts bearing relatively labile first-row transition metals; it was deemed necessary to stabilize the bond trans to the metal-�oxo� vector with oxidatively stable multidentate ligands (e.g., [CoII(PY5 )(OH2)]2+) to provide access to a high-valent and catalytically active species. This presentation will detail these findings, and also show how the role of a common sacrificial oxidant, (NH4)2[CeIV(NO3)6], can have unexpected effects in catalysis.

Mechanistic investigations of molecular water oxidation catalysis

246th National Meeting (2013)

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