Fluoro and Trifluoromethyl Derivatives of POCOP-Type Pincer Complexes of Nickel: Preparation and Reactivities in S<sub>N</sub>2 Fluorination and Direct Benzylation of Unactivated Arenes
Bibliographic record
Abstract
This report describes the synthesis, characterization, and reactivities of the pincer-type complexes κ P,κ C,κ P -(R-POCOP)NiX (R-POCOP = 2,6-( i -Pr 2 PO) 2,4-R-C 6 H 3; R = H, X = F ( 2a ), CF 3 ( 3a ); R = OMe, X = F ( 2b ), X = CF 3 ( 3b )). These complexes were prepared by treating their Ni–Br analogues with excess AgF at rt ( 2a and 2b ) or excess AgF and Me 3 SiCF 3 ( 3a and 3b ) at 45 °C. The Ni–F derivative 2a was shown to be an intermediate for the formation of the Ni–CF 3 derivative 3a . Complexes 2a, 3a, and 3b were fully characterized by multinuclear NMR spectroscopy, cyclic voltammetry, and X-ray diffraction analysis. Variable temperature, multinuclear NMR analysis of 2a helped elucidate interaction of the fluoride ligand with hydrofluoric acid present in the reaction medium. The bromo complexes 1a or 1b catalyzed fluorination of benzyl halides at 90 °C in the presence of excess AgF, whereas the Ni–CF 3 complexes 3 failed to promote trifluoromethylation of benzyl bromide, leading instead to a direct benzylation of the aromatic reaction solvent (benzene, toluene, xylene, or bromobenzene). Possible mechanisms for this benzylation reaction have been probed and discussed.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot 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.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
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.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
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".