Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 21, Pages 6758-6761Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b03977
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Funding
- MINECO [CTQ2014-57761-R, CTQ-2013-49075-R, SEV-2013-0319, CTQ2014-52974-REDC]
- ICIQ Foundation
- EU COST actions [CM1202, CM1205]
- Severo Ochoa pre-doctoral training fellowship [SVP-2014-068662]
- La Caixa Foundation
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A new family of tetra-anionic tetradentate amidate ligands, N-1,N1'-(1,2-phenylene)bis(N2-methyloxalamide) (H(4)L1), and its derivatives containing electron-donating groups at the aromatic ring have been prepared and characterized, together with their corresponding anionic Cu(II) complexes, [(LY)Cu](2-). At pH 11.5, the latter undergoes a reversible metal-based III/II oxidation process at 0.56 V and a ligand-based pH-dependent electron-transfer process at 1.25 V, associated with a large electrocatalytic water oxidation wave (overpotential of 700 mV). Foot-of-the-wave analysis gives a catalytic rate constant of 3.6 s(-1) at pH 11.5 and 12 s(-1) at pH 12.5. As the electron-donating capacity at the aromatic ring increases, the overpotential is drastically reduced down to a record low of 170 mV. In addition, DFT calculations allow us to propose a complete catalytic cycle that uncovers an unprecedented pathway in which crucial O-O bond formation occurs in a two-step, one-electron process where the peroxo intermediate generated has no formal M-O bond but is strongly hydrogen bonded to the auxiliary ligand.
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