<i>N</i>-Arylcyano-β-diketiminate Methallyl Nickel Complexes: Synthesis, Adduct Formation, and Reactivity toward Ethylene
Bibliographic record
Abstract
The syntheses and structures of new bis -N -phenyl-4-cyano-β-diketiminate ( 1 ), bis -N -phenyl-2-cyano-β-diketiminate ( 2 ), N -phenyl-4-cyano- N -phenyl-2-cyano - β-diketiminate ( 3 ), N -phenyl-4-cyano- N -2,6-diisopropylphenyl-β-diketiminate ( 4 ), N -phenyl-2-cyano- N -2,6-diisopropylphenyl-β-diketiminate ( 5 ), and methallyl nickel complexes [L 1 Ni(η 3 -methallyl)] ( 6 ), [L 2 Ni(η 3 -methallyl)] ( 7 ), [L 4 Ni(η 3 -methallyl)] ( 8 ), and [L 5 Ni(η 3 -methallyl)] ( 9 ) from the reaction of deprotonated ligands 1 / 2, 4 / 5, and methallylnickel chloride dimer are reported. Subsequent reactions of complexes 6 – 9 with tris(pentafluorophenyl)boron give rise to new adducts [L 1 Ni(η 3 -methallyl)]·2B(C 6 F 5 ) 3 ( 10 ), [L 2 Ni(η 3 -methallyl)]·2B(C 6 F 5 ) 3 ( 11 ), [L 4 Ni(η 3 -methallyl)]·B(C 6 F 5 ) 3 ( 12 ), and [L 5 Ni(η 3 -methallyl)]·B(C 6 F 5 ) 3 ( 13 ), where B(C 6 F 5 ) 3 is coordinated to the cyano group. New compounds are characterized by NMR, IR, and mass spectrometry techniques, and crystal structures of most compounds are obtained and described. Complexes 6 – 9, adducts 10 – 13, and adducts 10 – 13 with 5 equiv of B(C 6 F 5 ) 3 have been investigated toward ethylene activation. Complexes 6 – 9 were inactive toward ethylene even at 60 °C, while adducts 10 – 13 showed reactivity toward ethylene; adding 5 equiv of B(C 6 F 5 ) 3 to adducts 10 – 13 leads to an increase in reactivity toward ethylene. Adducts 10 and 11 alone and with 5 equiv of B(C 6 F 5 ) 3 catalyze the oligomer formation, while adducts 12 and 13 by the same conditions catalyze the polyethylene formation. Adduct 13 activity is five times higher with respect to 12 at 50 °C and two times higher at 70 °C. The formation of branched moderate molecular weight PE by 12 /B(C 6 F 5 ) 3 and 13 /B(C 6 F 5 ) 3 is observed.
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.
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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.015 | 0.001 |
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".