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Record W4394924263 · doi:10.1002/047084289x.rn02576

Palladium, [ <i>N</i> , <i>N</i> ′‐1,2‐ethanediylidenebis[2,6‐dimethylbenzenamine‐κN]][(3,4‐ <i>η</i> )‐2,5‐furandione] ( <sup>DMP</sup> DAB–Pd–MAH)

2024· other· en· W4394924263 on OpenAlexaff
David C. Leitch, Gilian T. Thomas

Bibliographic record

VenueEncyclopedia of Reagents for Organic Synthesis · 2024
Typeother
Languageen
FieldChemistry
TopicCatalytic C–H Functionalization Methods
Canadian institutionsUniversity of Victoria
Fundersnot available
KeywordsPalladiumChemistryDiethyl etherChloroformTetrahydrofuranMedicinal chemistryDiimineDichloromethaneAcetonitrileAcetoneEtherTolueneMaleic anhydrideDimethylformamideMethanolNuclear chemistrySolventOrganic chemistryCatalysis

Abstract

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image [2721487‐84‐7] C 22 H 22 N 2 O 3 Pd (MW 468.85) InChI = 1S/C18H20N2.C4H2O3.Pd/c1‐13‐7‐5‐8‐14(2)17(13)19‐11‐12‐20‐18‐15(3)9‐6‐10‐16(18)4;5‐3‐1‐2‐4(6)7‐3;/h5‐12H,1‐4H3;1‐2H;/b19‐11+,20‐12+;; InChiKey = WHOQNDZHEHSRKP‐GAMUHHASSA‐N (palladium(0) compound used as a precursor to phosphine palladium(0) complexes, 1–5 and as a catalyst precursor for cross‐coupling reactions, 1,6 CH activation reactions, 7 and enantioselective allylation reactions 4,8 ) Alternative Names : (1 E ,2 E )‐ N 1, N 2‐bis(2,6‐dimethylphenyl)ethane‐1,2‐diimine 2,5‐dihydrofuran‐2,5‐dione palladium, [κ 2 ‐ N , N ′‐bis(2,6‐dimethylphenyl)ethan‐1,2‐diimine][ η 2 ‐maleic anhydride]palladium(0). Physical Data : m.p. 121 °C (dec). Solubility : fully soluble (≥20 mg mL −1 ) in acetone, dichloromethane, tetrahydrofuran (THF), 2‐methyltetrahydrofuran (MeTHF); partially soluble in toluene (5 mg mL −1 ), ethyl acetate (2.5 mg mL −1 ); poorly soluble (≤2 mg mL −1 ) in pentane, n ‐hexane, n ‐heptane, diethyl ether, tert ‐butylmethyl ether (TBME); insoluble in isopropanol (&lt;1 mg mL −1 ); soluble but decomposes in acetonitrile, chloroform; poorly soluble and decomoposes in dimethylsulfoxide (DMSO), N,N ‐dimethylformamide (DMF), methanol, ethanol; insoluble in water. Form Supplied in : red/purple crystalline solid. Preparative Methods : commercially available. There are two reported procedures 1 for preparing DMP DAB–Pd–MAH by reacting N , N ′‐1,2‐ethanediylidenebis(2,6‐dimethylbenzenamine) ( DMP DAB) and maleic anhydride (MAH) 9 with either Pd 2 dba 3 ·CHCl 3 10 or “Pd(dba) 2 ” (actually Pd 2 dba 3 ·dba). 11 These palladium sources can be prepared from a variety of palladium(II) starting materials according to the method of Zalesskiy and Ananikov, 12 or purchased from commercial sources. Recystallization of crude “Pd(dba) 2 ” is not required, since purification of DMP DAB–Pd–MAH removes residual dba and colloidal palladium(0) (see below). N , N ′‐1,2‐ethanediylidenebis(2,6‐dimethylbenzenamine) ( DMP DAB) is prepared from glyoxal (40% wt/wt solution in water) and 2,6‐dimethylaniline in methanol with 13 or without 14 formic acid as a catalyst. Purification : colloidal palladium(0) can be removed from DMP DAB–Pd–MAH by dissolving the solid in a minimum amount of acetone, dichloromethane, or THF, followed by filtration through a bed of Celite ™ and subsequent solvent removal from the filtrate. Uncoordinated N , N ′‐1,2‐ethanediylidenebis(2,6‐dimethylbenzenamine) ( DMP DAB), maleic anhydride, and/or residual dibenzylideneacetone (dba) from the synthesis can be removed by slurrying solid DMP DAB–Pd–MAH in TBME (∼30 mL g −1 of solid), followed by filtration and washing with TBME. Analysis of Reagent Purity : 1 H NMR spectroscopic analysis is suitable for routine purity determination. In d 6 ‐acetone (solvent residual peak at 2.05 ppm), DMP DAB–Pd–MAH has diagnostic resonances at 8.55 ppm (s, 2 H ) for the N=CH–CH=N protons, 3.57 ppm (s, 2 H ) for the coordinated male

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)0.004
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 score0.073
Threshold uncertainty score1.000

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0010.004
Meta-epidemiology (narrow)0.0020.002
Meta-epidemiology (broad)0.0020.001
Bibliometrics0.0010.001
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0020.000
Research integrity0.0020.001
Insufficient payload (model declined to judge)0.0750.003

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 head0.013
GPT teacher head0.255
Teacher spread0.242 · 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".

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Citations0
Published2024
Admission routes1
Has abstractyes

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Same venueEncyclopedia of Reagents for Organic SynthesisSame topicCatalytic C–H Functionalization MethodsFrench-language works237,207