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Record W2074473525 · doi:10.1039/c3dt53495b

Ligand-based molecular recognition and dioxygen splitting: an endo epoxide ending

2014· article· en· W2074473525 on OpenAlexafffund
Peter E. Sues, Matthew W. Forbes, Alan J. Lough, Robert H. Morris

Bibliographic record

VenueDalton Transactions · 2014
Typearticle
Languageen
FieldChemistry
TopicOxidative Organic Chemistry Reactions
Canadian institutionsUniversity of Toronto
FundersNatural Sciences and Engineering Research Council of Canada
KeywordsEpoxideLigand (biochemistry)ChemistryStereochemistryPhotochemistryCombinatorial chemistryOrganic chemistryCatalysisBiochemistryReceptor

Abstract

fetched live from OpenAlex

The phosphido complex RuCp*(PPh2CH=CHPPh2)(PPh2) (1) was exposed to a number of small molecules and was found to recognize and activate molecular oxygen in an unprecedented fashion: the ruthenium species split O2 in a ligand-based 4-electron reduction to produce an endo epoxide, as well as a phosphinito ligand. Based on XRD data, VT NMR studies, cyclooctene trapping studies, and crossover experiments it was determined that the reaction proceeded through an intramolecular mechanism in which initial oxidation of the phosphido ligand generated an end-on peroxo intermediate. This mechanism was also supported by computational studies and electrochemical experiments. In contrast, an analogue of 1, RuCp*(Ph2P(ortho-C6H4)PPh2)(PPh2) (3), reacted in an intermolecular fashion to generate two phosphinito ligands.

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 categoriesMeta-epidemiology (narrow), Insufficient payload (model declined to judge)
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 score0.098
Threshold uncertainty score1.000

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)0.0010.000

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 head0.021
GPT teacher head0.240
Teacher spread0.219 · 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.

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

Citations4
Published2014
Admission routes2
Has abstractyes

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