Decoding Proton-Coupled Electron Transfer with Potential-pKa Diagrams

Brian D. McCarthy, Jillian L. Dempsey

Research output: Contribution to journalArticle

  • 6 Citations

Abstract

Aqueous potential-pH diagrams, commonly called Pourbaix diagrams, were originally developed to study metal corrosion in the 1930s and 1940s. Pourbaix diagrams have since been widely adopted for use across chemistry disciplines, particularly for the study of aqueous proton-coupled electron transfer reactions. Despite this enormous versatility, a clear extension of analogous diagrams to nonaqueous solvents is lacking. The problem hinges on the difficulty of defining the nonaqueous solution pH. Here, we address this issue by reporting the development of diagrams based on nonaqueous pKa scales. We experimentally construct diagrams for two transition-metal complexes that undergo proton-coupled electron transfer reactivity by recording their reduction potentials in the presence of acids with varying pKa values. These experimental diagrams validate the potential-pKa theory and provide valuable thermochemical information for proton-coupled electron transfer reactions, including for fleetingly stable species.

LanguageEnglish (US)
Pages1225-1231
Number of pages7
JournalInorganic Chemistry
Volume56
Issue number3
DOIs
StatePublished - Feb 6 2017

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decoding
Decoding
Protons
electron transfer
diagrams
protons
Electrons
Coordination Complexes
Hinges
Transition metals
Corrosion
Acids
hinges
versatility
corrosion
reactivity
transition metals
recording
chemistry
acids

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Decoding Proton-Coupled Electron Transfer with Potential-pKa Diagrams. / McCarthy, Brian D.; Dempsey, Jillian L.

In: Inorganic Chemistry, Vol. 56, No. 3, 06.02.2017, p. 1225-1231.

Research output: Contribution to journalArticle

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