Journal
CHEMPHYSCHEM
Volume 10, Issue 1, Pages 191-198Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.200800361
Keywords
cyclic voltammetry; electrochemistry; electron transfer; oxidation; proton transfer
Funding
- ANR
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Successive oxidation of transition metal(II) aqua complexes ((MOH2)-O-II to (MOH)-O-III) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial Systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from on aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the some complex attached to on electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.
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