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Kinetic and Mechanistic Characterization of Low-Overpotential, H2O2-Selective Reduction of O2 Catalyzed by N2O2-Ligated Cobalt Complexes

  • Yu-Heng Wang
    Yu-Heng Wang
    Department of Chemistry, University of Wisconsin—Madison, Madison, Wisconsin 53706, United States
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  • , 
  • Zachary K. Goldsmith
    Zachary K. Goldsmith
    Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States
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  • , 
  • Patrick E. Schneider
    Patrick E. Schneider
    Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States
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  • , 
  • Colin W. Anson
    Colin W. Anson
    Department of Chemistry, University of Wisconsin—Madison, Madison, Wisconsin 53706, United States
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  • , 
  • James B. Gerken
    James B. Gerken
    Department of Chemistry, University of Wisconsin—Madison, Madison, Wisconsin 53706, United States
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  • , 
  • Soumya Ghosh
    Soumya Ghosh
    Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States
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  • , 
  • Sharon Hammes-Schiffer*
    Sharon Hammes-Schiffer
    Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States
    *[email protected]
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    Orcidhttp://orcid.org/0000-0002-3782-6995
  • , and 
  • Shannon S. Stahl*
    Shannon S. Stahl
    Department of Chemistry, University of Wisconsin—Madison, Madison, Wisconsin 53706, United States
    *[email protected]
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    Orcidhttp://orcid.org/0000-0002-9000-7665
Cite this: J. Am. Chem. Soc. 2018, 140, 34, 10890–10899
Publication Date (Web):July 30, 2018
https://doi.org/10.1021/jacs.8b06394
Copyright © 2018 American Chemical Society
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    Abstract

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    A soluble, bis-ketiminate-ligated Co complex [Co(N2O2)] was recently shown to catalyze selective reduction of O2 to H2O2 with an overpotential as low as 90 mV. Here we report experimental and computational mechanistic studies of the Co(N2O2)-catalyzed O2 reduction reaction (ORR) with decamethylferrocene (Fc*) as the reductant in the presence of AcOH in MeOH. Analysis of the Co/O2 binding stoichiometry and kinetic studies support an O2 reduction pathway involving a mononuclear cobalt species. The catalytic rate exhibits a first-order kinetic dependence on [Co(N2O2)] and [AcOH], but no dependence on [Fc*] or [O2]. Differential pulse voltammetry and computational studies support CoIII-hydroperoxide as the catalyst resting state and protonation of this species as the rate-limiting step of the catalytic reaction. These results contrast previous mechanisms proposed for other Co-catalyzed ORR systems, which commonly feature rate-limiting protonation of a CoIII-superoxide adduct earlier in the catalytic cycle. Computational studies show that protonation is strongly favored at the proximal oxygen of the CoIII(OOH) species, accounting for the high selectivity for formation of hydrogen peroxide. Further analysis shows that a weak dependence of the ORR rate on the pKa values of the protonated CoIII(OOH) species across a series of Co(N2O2) catalysts provides a rationale for the unusually low overpotential observed for O2 reduction to H2O2.

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