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Issue 2, 2013
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Proton-coupled electron transfer at a [Co-OHx]z unit in aqueous media: evidence for a concerted mechanism

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Abstract

The proton-coupled electron transfer (PCET) chemistry associated with the [Co-OH]2+/[Co-OH2]2+ redox couple for [Co(PY5)(OH2)]2+ (1; PY5 = 2,6-(bis(bis-2-pyridyl)-methoxymethane)-pyridine) and [CoII(pz4depy)(OH2)]2+ (2; pz4depy = 2,6-bis(1,1-di(1H-pyrazol-1-yl)ethyl)pyridine) is reported. It is found that the couple is acutely sensitive to the geometry of the axially ligated group in addition to the electronic-donating/-withdrawing character of the ligand. Interrogation of the electron-transfer kinetics by electrochemical methods also shows for the first time that the interconversion of [CoIII-OH]2+ and [CoII-OH2]2+ proceeds through a concerted pathway in favour of energetically unfavourable stepwise electron-transfer or proton-transfer reaction steps.

Graphical abstract: Proton-coupled electron transfer at a [Co-OHx]z unit in aqueous media: evidence for a concerted mechanism

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Publication details

The article was received on 02 Sep 2012, accepted on 13 Nov 2012 and first published on 04 Dec 2012


Article type: Edge Article
DOI: 10.1039/C2SC21419A
Chem. Sci., 2013,4, 734-738

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    Proton-coupled electron transfer at a [Co-OHx]z unit in aqueous media: evidence for a concerted mechanism

    D. J. Wasylenko, H. M. Tatlock, L. S. Bhandari, J. R. Gardinier and C. P. Berlinguette, Chem. Sci., 2013, 4, 734
    DOI: 10.1039/C2SC21419A

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