Regioselective Hydroamination of Acrylonitrile Catalyzed by Cationic Pincer Complexes of Nickel(II)
Why this work is in the frame
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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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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.012 | 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 it