Regioselective Hydroamination of Acrylonitrile Catalyzed by Cationic Pincer Complexes of Nickel(II)
Bibliographic record
Abstract
The cationic pincer-type complexes [{( i -Pr 2 PCH 2 CH 2 ) 2 CH}Ni(NCCH 3 )][BPh 4 ] ( 1 ), [{2,6-( i -Pr 2 PCH 2 ) 2 -C 6 H 3 }Ni(NCCH 3 )][BPh 4 ] ( 2 ), [{2,6-( i -Pr 2 PO) 2 -C 6 H 3 }Ni(NCCH 3 )][BPh 4 ] ( 3 ), and [{2,6-( i -Pr 2 PO) 2 -3,5-Cl 2 -C 6 H}Ni(NCCH 3 )][BPh 4 ] ( 6 ) have been prepared and fully characterized by NMR spectroscopy and X-ray crystallography. Cyclic voltammetry measurements of the Ni−Br precursors of 2, 3, and 6 indicated that substituting the CH 2 moiety in the ligand skeleton by O, or some of the aromatic protons by Cl, renders the metal center less susceptible to oxidation. Evaluating the catalytic activities of 1 − 3, 6, and the t -Bu analogue of 1 for addition of aniline to acrylonitrile showed 3 to be the most competent catalyst precursor. Isolation of [{( t -Bu 2 PCH 2 CH 2 ) 2 CH}Ni(NCCH 2 CH 2 NHPh)][BPh 4 ] ( 7 ) from the reaction of [{( t -Bu 2 PCH 2 CH 2 ) 2 CH}Ni(NCCH═CH 2 )][BPh 4 ] with aniline suggests that these cationic precursors act as Lewis acids that bind the nitrile moiety of acrylonitrile, thereby activating the olefinic moiety toward nucleophilic attack by aniline.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 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 | 0.001 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 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 source (direct Gemma or distilled Codex), 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".