Hydroamination and Alcoholysis of Acrylonitrile Promoted by the Pincer Complex {κ<sup><i>P</i></sup>,κ<sup><i>C</i></sup>,κ<sup><i>P</i></sup>-2,6-(Ph<sub>2</sub>PO)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>}Ni(OSO<sub>2</sub>CF<sub>3</sub>)
Bibliographic record
Abstract
This report describes the catalytic activity of the pincer-type complex {κ P,κ C,κ P -2,6-(Ph 2 PO) 2 C 6 H 3 }Ni(OSO 2 CF 3 ) ( 1 ) in the anti-Markovnikov addition of aliphatic and aromatic amines and alcohols to acrylonitrile, crotonitrile, and methacrylonitrile. The influence of additives on the catalytic activities was investigated, and it was found that substoichiometric quantities of water promoted the C–N bond forming reactions catalyzed by 1, especially the reactions involving aromatic amines; in comparison, NEt 3 had a less dramatic impact. The opposite pattern was observed for the alcoholysis of acrylonitrile promoted by 1: water had no beneficial effect on these reactions, while NEt 3 proved to be a potent promoter. Another important difference between these reactions is that hydroamination works better with more nucleophilic amines, whereas the alcoholysis reactions work well with ArOH, CF 3 CH 2 OH, and ArCH 2 OH but not at all with the more nucleophilic aliphatic alcohols methanol, ethanol, and 2-propanol. Both hydroamination and alcoholysis proceed much better with acrylonitrile in comparison to its Me-substituted derivatives crotonitrile and methacrylonitrile. Under optimized conditions, precatalyst 1 promotes conjugate additions to acrylonitrile with catalytic turnover numbers of up to 100 (hydroamination) or higher (alcoholysis). Spectroscopic studies have established that the main Ni-containing species in the hydroamination reactions is a cationic adduct in which the olefinic substrate is bound to the Ni center via its nitrile moiety; this binding activates the double bond toward an outer-sphere nucleophilic attack by the amine (Michael addition). The solid-state structures of the cationic nitrile adducts [{κ P,κ C,κ P -2,6-(Ph 2 PO) 2 C 6 H 3 }Ni(NCR)][OSO 2 CF 3 ] (R = Me ( 2a ), CH 2 CH 2 N(H)Ph ( 2e )), which can be regarded as model complexes for the species involved in the hydroamination catalysis, have been elucidated. Also reported are the solid-state structures of the charge-neutral compound {κ P,κ C,κ P -2,6-( i -Pr 2 PO) 2 C 6 H 3 }Ni(OSO 2 CF 3 ) and an octahedral Ni(II) species resulting from the aerobic/hydrolytic oxidation of 1 .
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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) | 0.000 | 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) | 0.001 | 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".