One-electron oxidation of intramolecularly hydrogen-bonded phenol-base compounds typically proceeds by concerted proton-electron transfer (CPET), one type of proton-coupled electron transfer (PCET). Rate constants as a function of driving force have been measured for a wide range of oxidants and bases, from second to nanosecond timescales. The results are overall well interpreted using Marcus theory, which gives insights into the driving force dependence of the rate constants, into how structure affects CPET intrinsic barriers, and into the non-adiabaticity of the reactions. We will also discuss the challenges of obtaining the detailed parameters needed for deeper insights in these systems, for instance through application of Hammes-Schiffer's Multistate Continuum Theory. Preliminary results from a fully unimolecular photo-induced CPET system will also be presented.

Using phenol-base compounds to probe multiple site proton-coupled electron transfer

248th National Meeting (2014)

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