XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex
Authors
Levin, Natalia
Casadevall, Carla
Cutsail, George E., III
Lloret‐Fillol, Julio
DeBeer, Serena
Publication Date
2021-12-27Journal Title
ChemElectroChem
ISSN
2196-0216
Language
en
Type
Other
This Version
AO
VoR
Metadata
Show full item recordCitation
Levin, N., Casadevall, C., Cutsail, G. E. I., Lloret‐Fillol, J., DeBeer, S., & Rüdiger, O. (2021). XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex. [Other]. https://doi.org/10.1002/celc.202101271
Description
Funder: Max-Planck-Gesellschaft; Id: http://dx.doi.org/10.13039/501100004189
Funder: ICIQ Fundation
Abstract
Abstract: In this study, we combine in situ spectroelectrochemistry coupled with electron paramagnetic resonance (EPR) and X‐ray absorption spectroscopies (XAS) to investigate a molecular Ru‐based water oxidation catalyst bearing a polypyridinic backbone [RuII(OH2)(Py2Metacn)]2+. Although high valent key intermediate species arising in catalytic cycles of this family of compounds have remain elusive due to the lack of additional anionic ligands that could potentially stabilize them, mechanistic studies performed on this system proposed a water nucleophilic attack (WNA) mechanism for the O−O bond formation. Employing in situ experimental conditions and complementary spectroscopic techniques allowed to observe intermediates that provide support for a WNA mechanism, including for the first time a Ru(V) oxo intermediate based on the Py2Metacn ligand, in agreement with the previously proposed mechanism.
Keywords
Communication, Communications, spectroelectrochemistry, water oxidation, ruthenium, catalyst, in situ electrochemistry
Sponsorship
Mountain Equipment Co-op (FPU14/02550)
European Research Council (FP7-PEOPLE-2010-ERG-268445)
Ministerio de Ciencia e Innovación (PID2019-110050RB-I00)
Identifiers
celc202101271
External DOI: https://doi.org/10.1002/celc.202101271
This record's DOI: https://doi.org/10.17863/CAM.79790
Rights
Licence:
http://creativecommons.org/licenses/by-nc/4.0/
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