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Record W3211392261 · doi:10.1002/celc.202101271

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

2021· article· en· W3211392261 on OpenAlexfundno aff
Natalia Levin, Carla Casadevall, George E. Cutsail, Julio Lloret‐Fillol, Serena DeBeer, Olaf Rüdiger

Bibliographic record

VenueChemElectroChem · 2021
Typearticle
Languageen
FieldEnergy
TopicElectrocatalysts for Energy Conversion
Canadian institutionsnot available
FundersSLAC National Accelerator LaboratoryAgencia Estatal de InvestigaciónOffice of ScienceMinisterio de Ciencia e InnovaciónBasic Energy SciencesPaul Scherrer InstitutEuropean Research CouncilMountain Equipment Co-operativeFP7 People: Marie-Curie ActionsMinisterio de Economía y CompetitividadMax-Planck-GesellschaftInstitut Català d'Investigació QuímicaU.S. Department of Energy
KeywordsElectron paramagnetic resonanceX-ray absorption spectroscopyIn situChemistryCatalysisPhotochemistryLigand (biochemistry)RutheniumNucleophileReaction intermediateAbsorption spectroscopyCrystallographyNuclear magnetic resonanceOrganic chemistry

Abstract

fetched live from OpenAlex

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 [Ru II (OH 2 )(Py 2 Metacn)] 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 Py 2 Metacn ligand, in agreement with the previously proposed mechanism.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.019
Threshold uncertainty score0.708

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.015
GPT teacher head0.226
Teacher spread0.211 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

The models applied no category: nothing in the taxonomy fit this work.
Study designBench or experimental
Domainnot available
GenreEmpirical

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations13
Published2021
Admission routes1
Has abstractyes

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