Electronic Design Criteria for O−O Bond Formation via Metal−Oxo Complexes

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Abstract
Metal−oxos are critical intermediates for the management of oxygen and its activation. The reactivity of the metal−oxo is central to the formation of O−O bonds, which is the essential step for oxygen generation. Two basic strategies for the formation of O−O bonds at metal−oxo active sites are presented. The acid–base (AB) strategy involves the attack of a nucleophilic oxygen species (e.g., hydroxide) on an electrophilic metal−oxo. Here, active-site designs must incorporate the assembly of a hydroxide (or water) proximate to a high-valent metal−oxo of even d electron count. For the radical coupling (RC) strategy, two high-valent metal−oxos of an odd d electron count are needed to drive O−O coupling. This Forum Article focuses on the different electronic structures of terminal metal−oxos that support AB and RC strategies and the design of ligand scaffolds that engender these electronic structures.