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Issue 7, 2012
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Using combinations of oxidants and bases as PCET reactants: thermochemical and practical considerations

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Abstract

Studies in proton-coupled electron transfer (PCET) often require the combination of an outer-sphere oxidant and a base, to remove an electron and a proton. A common problem is the incompatibility of the oxidant and the base, because the former is electron deficient and the latter electron rich. We have tested a variety of reagents and report a number of oxidant/base combinations that are compatible and therefore potentially useful as PCET reagents. A formal bond dissociation free energy (BDFE) for a reagent combination is defined by the redox potential of the oxidant and pKa of the base. This is a formal BDFE because no X–H bond is homolytically cleaved, but it is a very useful way to categorize the H accepting ability of an oxidant/base PCET pair. Formal BDFEs of stable oxidant/base combinations range from 71 to at least 98 kcal mol−1. Effects of solvent, concentration, temperature, and counterions on the stability of the oxidant/base combinations are discussed. Extensions to catalysis and related reductant/acid combinations are mentioned.

Graphical abstract: Using combinations of oxidants and bases as PCET reactants: thermochemical and practical considerations

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Publication details

The article was received on 27 Nov 2011, accepted on 08 Feb 2012 and first published on 21 Feb 2012


Article type: Paper
DOI: 10.1039/C2EE03300C
Citation: Energy Environ. Sci., 2012,5, 7771-7780
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    Using combinations of oxidants and bases as PCET reactants: thermochemical and practical considerations

    C. R. Waidmann, A. J. M. Miller, C. A. Ng, M. L. Scheuermann, T. R. Porter, T. A. Tronic and J. M. Mayer, Energy Environ. Sci., 2012, 5, 7771
    DOI: 10.1039/C2EE03300C

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