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Record W1930877996 · doi:10.1139/cjc-2015-0251

Systematic dismantling of a carefully designed PC<sub>carbene</sub>P pincer ligand via C–C bond activations at an iridium centre

2015· article· en· W1930877996 on OpenAlexafffundvenue
Joel D. Smith, Javier Borau‐Garcia, Warren E. Piers, Denis M. Spasyuk

Bibliographic record

VenueCanadian Journal of Chemistry · 2015
Typearticle
Languageen
FieldChemistry
TopicCatalytic Cross-Coupling Reactions
Canadian institutionsUniversity of Calgary
FundersNatural Sciences and Engineering Research Council of CanadaCanada Research Chairs
KeywordsChemistryCarbeneDecarbonylationPhosphineLigand (biochemistry)IridiumPincer ligandHydrogenolysisMedicinal chemistryBond cleavagePhotochemistryStereochemistryPincer movementCatalysisOrganic chemistry

Abstract

fetched live from OpenAlex

An electron-rich PC sp2 P ligand, incorporating N,N-dimethylamino groups para to the anchoring carbene donor of the ligand, was prepared and coordinated to iridium, producing the iridium carbene chloride 2. This species undergoes facile reaction with N 2 O to afford an iridaepoxide complex, 3, in which an oxygen atom has been transferred to the Ir=C bond. The rate of this reaction is significantly faster than that observed for the less electron rich, unsubstituted ligand. However, further reaction of 3 involving cleavage of one of the ligand C–C bonds was observed, producing the bis-phosphine chorido complex 4. This process was accelerated by the presence of H 2 . Heating 4 under H 2 resulted in hydrogenolysis of the ortho-metalated phosphine ligand to give a hydrido complex (5) and decarbonylation of the acyl phosphine ligand to give, finally, Vaska’s complex analog 6. All compounds were fully characterized, and the sequence represents the dismantling of the PC sp2 P ligand framework.

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)0.001
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 score0.002
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.001
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0010.000
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 head0.228
Teacher spread0.213 · 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

Citations17
Published2015
Admission routes3
Has abstractyes

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