dc.contributor.author |
Garrido-Barros, Pablo |
dc.contributor.author |
Funes-Ardoiz, Ignacio |
dc.contributor.author |
Drouet, Samuel |
dc.contributor.author |
Benet-Buchholz, Jordi |
dc.contributor.author |
Maseras, Feliu |
dc.contributor.author |
Llobet, Antoni |
dc.date.accessioned |
2018-01-15T16:04:31Z |
dc.date.accessioned |
2018-02-15T10:27:51Z |
dc.date.available |
2018-01-15T16:04:31Z |
dc.date.available |
2018-02-15T10:27:51Z |
dc.date.issued |
2015 |
dc.identifier.uri |
http://hdl.handle.net/2072/226359 |
dc.identifier.uri |
http://hdl.handle.net/2072/305798 |
dc.language.iso |
eng |
dc.publisher |
American Chemical Society |
dc.relation |
MINECO with FEDER Funds |
dc.relation |
Proyectos I+D+I - Retos 2013 |
dc.relation |
Severo Ochoa Excellence Accreditation 2014-2018 |
dc.relation |
PRO-H |
dc.relation.ispartof |
Journal of The American Chemical Society |
dc.rights |
Copyright © 2015 American Chemical Society |
dc.title |
Redox Non-innocent Ligand Controls Water Oxidation Overpotential in a New Family of Mononuclear Cu-Based Efficient Catalysts |
dc.type |
info:eu-repo/semantics/article |
dc.relation.projectID |
CTQ2013-49075-R |
dc.relation.projectID |
SEV2013-0319 |
dc.relation.projectID |
CTQ2014-52974-REDC |
dc.identifier.doi |
https://dx.doi.org/10.1021/jacs.5b03977 |
dc.rights.accessLevel |
info:eu-repo/semantics/openAccess |
dc.description.abstract |
A new family of tetra-anionic tetradentate amidate ligands, N1,N1′-(1,2-phenylene)bis(N2-methyloxalamide) (H4L1), 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. |