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Co(salophen)-Catalyzed Aerobic Oxidation of p‑Hydroquinone: Mechanism and Implications for Aerobic Oxidation Catalysis

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journal contribution
posted on 29.02.2016, 00:00 by Colin W. Anson, Soumya Ghosh, Sharon Hammes-Schiffer, Shannon S. Stahl
Macrocyclic metal complexes and p-benzoquinones are commonly used as co-catalytic redox mediators in aerobic oxidation reactions. In an effort to gain insight into the mechanism and energetic efficiency of these reactions, we investigated Co­(salophen)-catalyzed aerobic oxidation of p-hydroquinone. Kinetic and spectroscopic data suggest that the catalyst resting-state consists of an equilibrium between a CoII(salophen) complex, a CoIII-superoxide adduct, and a hydrogen-bonded adduct between the hydroquinone and the CoIII–O2 species. The kinetic data, together with density functional theory computational results, reveal that the turnover-limiting step involves proton-coupled electron transfer from a semi-hydroquinone species and a CoIII-hydroperoxide intermediate. Additional experimental and computational data suggest that a coordinated H2O2 intermediate oxidizes a second equivalent of hydroquinone. Collectively, the results show how Co­(salophen) and p-hydroquinone operate synergistically to mediate O2 reduction and generate the reactive p-benzoquinone co-catalyst.