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Record W2059299121 · doi:10.1039/b606167b

Can one oxidize an atom by reducing the molecule that contains it?

2006· article· en· W2059299121 on OpenAlexafffund
Paul W. Ayers

Bibliographic record

VenuePhysical Chemistry Chemical Physics · 2006
Typearticle
Languageen
FieldMaterials Science
TopicPorphyrin and Phthalocyanine Chemistry
Canadian institutionsMcMaster University
FundersNatural Sciences and Engineering Research Council of CanadaCanada Research Chairs
KeywordsChemistryFukui functionMoleculeMetalRedoxChemical physicsAtom (system on chip)Ligand (biochemistry)Computational chemistryInorganic chemistryElectrophileCatalysisOrganic chemistry

Abstract

fetched live from OpenAlex

Negative values for the condensed Fukui function are identified as the key to designing molecules in which reduction of the molecule is associated with oxidation of one of the atomic centers, or vice versa. Sufficient conditions for negative condensed Fukui functions are derived, and metal complexes are identified as likely candidates for this exotic redox chemistry. Based on our theoretical understanding of where negative values of the Fukui function occur [P. W. Ayers, R. C. Morrison and R. K. Roy. J. Chem. Phys., 2002, 116, 8731], molecular-orbital diagrams for molecules where molecular oxidation is coupled to atomic reduction (or vice versa) are sketched. Whether one could design a metal complex with these properties is an open question but, if one could, then that compound would have fascinating redox chemistry and interesting magnetic properties. Candidate molecules for this property include metal complexes with small metal-to-ligand and/or ligand-to-metal charge transfer excitation energies.

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)
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 score0.013
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 science0.0010.000
Research integrity0.0000.001
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 head0.017
GPT teacher head0.242
Teacher spread0.225 · 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

Citations77
Published2006
Admission routes2
Has abstractyes

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