XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex**
- Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany)
- Institute of Chemical Research of Catalonia (ICIQ), Tarragona (Spain)
- Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany); University of Duisburg-Essen (Germany)
In this study, we combine in situ spectroelectrochemistry coupled with electron paramagnetic resonance (EPR) and X-ray absorption spectroscopies (XAS) to investigate a molecular Rubased 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
- Research Organization:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Max-Planck-Society; ICIQ Foundation; European Research Foundation
- Grant/Contract Number:
- AC02-76SF00515; FPU14/02550
- OSTI ID:
- 1903969
- Journal Information:
- ChemElectroChem, Vol. 9, Issue 3; ISSN 2196-0216
- Publisher:
- ChemPubSoc EuropeCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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