The history of organometallic chemistry during much of the 20th century was dominated by reductive and redox-neutral reactions, such as hydrogenation, hydroformylation, olefin polymerization and metathesis, and cross-coupling. The past couple decades have witnessed expansive growth in the development of organometallic oxidation reactions, including alcohol, alkene, and aromatic and aliphatic C–H oxidation reactions. This presentation will survey mechanistic foundations that contributed to these developments, including (a) principles that underlie effective use of O2 as a terminal oxidant, (b) how ancillary donor ligands can support oxidation catalysts, without attenuating the oxidation potential of the Pd catalyst, and (c) how first-row transition-metal catalysts, such as Cu, take advantage of one-electron redox steps to support two-electron oxidation reactions with O2 as a four-electron oxidant.

Award Address (ACS Award in Organometallic Chemistry sponsored by Dow). Organometallic aerobic oxidation catalysis

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