Electronic design criteria for O-O bond formation via metal-oxo complexes |
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Authors: | Betley Theodore A Wu Qin Van Voorhis Troy Nocera Daniel G |
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Institution: | Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA. |
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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. |
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