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>)
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
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 .
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.
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 | 0.005 | 0.004 |
| Meta-epidemiology (narrow) | 0.007 | 0.007 |
| Meta-epidemiology (broad) | 0.007 | 0.004 |
| Bibliometrics | 0.004 | 0.014 |
| Science and technology studies | 0.002 | 0.004 |
| Scholarly communication | 0.002 | 0.004 |
| Open science | 0.006 | 0.004 |
| Research integrity | 0.004 | 0.006 |
| Insufficient payload (model declined to judge) | 0.000 | 0.002 |
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