XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex**

Levin, Natalia; Casadevall, Carla; Cutsail III, George E.; Lloret‐Fillol, Julio; DeBeer, Serena; Rüdiger, Olaf

doi:10.1002/celc.202101271

XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex**

Journal Article · Mon Dec 27 00:00:00 EST 2021 · ChemElectroChem

DOI:https://doi.org/10.1002/celc.202101271· OSTI ID:1903969

Levin, Natalia ^[1]; Casadevall, Carla ^[2]; Cutsail III, George E. ^[3]; Lloret‐Fillol, Julio ^[2]; DeBeer, Serena ^[4]; ^[4]

Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany); OSTI
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)
Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (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 [Ru^II(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

View Accepted Manuscript (DOE)

Research Organization:: Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr (Germany); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: European Research Foundation; ICIQ Foundation; Max-Planck-Society; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1903969

Journal Information:: ChemElectroChem, Journal Name: ChemElectroChem Journal Issue: 3 Vol. 9; ISSN 2196-0216

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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XAS and EPR in Situ Observation of Ru(V) Oxo Intermediate in a Ru Water Oxidation Complex**

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