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Record W2137400048 · doi:10.1002/047084289x.rn01644

η<sup>5</sup>-Cyclopentadienyl-η<sup>3</sup>-1-phenylallylpalladium

2014· reference-entry· en· W2137400048 on OpenAlexaff
Andrew W. Fraser, Michael C. Baird

Bibliographic record

VenueEncyclopedia of Reagents for Organic Synthesis · 2014
Typereference-entry
Languageen
FieldChemistry
TopicCatalytic Cross-Coupling Reactions
Canadian institutionsQueen's University
Fundersnot available
KeywordsCyclopentadienyl complexRadiochemistryChemistryPhysics

Abstract

fetched live from OpenAlex

[105333-10-6] C14H14Pd (MW 288.68) InChI = 1S/C9H9.C5H5.Pd/c1-2-6-9-7-4-3-5-8-9;1-2-4-5-3-1;/h2-8H,1H2;1-5H; InChIKey = STDKYMKMBSTDJK-UHFFFAOYSA-N (reacts with a variety of phosphines L to reductively eliminate C14H14 and form palladium(0) compounds of the type PdL21. The latter are believed to be the catalytic species in many cross-coupling reactions, and η5-cyclopentadienyl-η3-1-phenylallylpalladium (I) is the only readily available precatalyst known to effect quantitative PdL2 formation for use in cross-coupling reactions1) Physical Data: mp 45 °C (dec.). Solubility: soluble in most types of organic solvents. Analysis of Reagent Purity: 1H NMR spectrum (600 MHz, toluene-d8): δ 2.16 (d, J 10.5 Hz, 1H), 3.36 (d, J 6.1 Hz, 1H), 3.84 (d, 9.8 Hz, 1H), 5.14 (ddd, J 6.1 Hz, 9.8 Hz, 10.5 Hz, 1H), 5.63 (s, 5H), 6.98–7.03 (m, 3H), 7.24–7.27 (m, 2H). Form Supplied in: deep purple-red crystals; commercially available. Preparative Methods:1 all steps were carried out under an atmosphere of purified argon using solvents dried by passage through activated alumina columns (Innovative Technology Solvent Purification System) and then stored over 3A molecular sieves dried under reduced pressure at 225 °C. A solution of sodium cyclopentadienide in THF (2.0 M, Aldrich) (1.45 mL, 2.90 mmol), diluted with 20 mL THF in a dropping funnel, was added dropwise to a stirred suspension of [Pd(η3-1-Ph-C3H4)Cl]22 (0.60 g, 1.16 mmol) in 20 mL THF at −78 °C. The resulting deep purple solution was stirred for 30 min, and then warmed to room temperature. The solvent was removed at room temperature under reduced pressure and the resulting solid product was extracted using three 20 mL portions of hexanes. The filtrate was reduced under reduced pressure, yielding an oily purple solid that was dissolved in ∼5 mL hexanes at room temperature. The resulting solution was cooled at −35 °C to give purple crystals that were collected by filtration. Yield: 0.565 g, 84%. Purple-red crystals can also be obtained by sublimation at 40 °C, 1 × 10−3 Torr. Handling, Storage, and Precautions: although heating during synthesis and workup can result in decomposition and palladium metal deposition, η5-cyclopentadienyl-η3-1-phenylallylpalladium (I) is, once prepared and purified, stable in solution for at least 30 min at 50 °C. Although long-term storage of I is probably best in a freezer, solutions are stable for several days under air at ambient temperatures.

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)0.001
metaresearch head score (Gemma)0.006
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow), Research integrity, Insufficient payload (model declined to judge)
Consensus categoriesMeta-epidemiology (narrow), Insufficient payload (model declined to judge)
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Not applicable · Consensus signal: Not applicable
GenreCandidate signal: Other · Consensus signal: Other
Teacher disagreement score0.212
Threshold uncertainty score0.999

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0010.006
Meta-epidemiology (narrow)0.0020.002
Meta-epidemiology (broad)0.0030.002
Bibliometrics0.0010.001
Science and technology studies0.0010.001
Scholarly communication0.0000.000
Open science0.0030.001
Research integrity0.0020.002
Insufficient payload (model declined to judge)0.0230.002

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 head0.253
Teacher spread0.238 · 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; both teacher heads agree on what is shown here.

Study designNot applicable
Domainnot available
GenreOther

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

Citations7
Published2014
Admission routes1
Has abstractyes

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