C<sub>6</sub>F<sub>5</sub>-Group Transfer from [MeB(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>]<sup>-</sup> to the Metal Center of L<sub>2</sub>MMe<sup>+</sup> (M = Ti, Zr) as a Deactivation Pathway in Olefin Polymerization Catalysis: A Combined Density Functional Theory and Molecular Mechanics Investigation
Bibliographic record
Abstract
We have carried out a combined density functional theory and molecular mechanics study of aryl group transfer reactions from [MeB(C 6 F 5 ) 3 ] - to the metal center of L 2 MMe + (M = Ti, Zr). This reaction, which produces L 2 MMe(C 6 F 5 ) and MeB(C 6 F 5 ) 2, is a possible deactivation pathway in metal-catalyzed single-site olefin polymerization. The cationic catalyst systems L 2 MMe + include (NPR 3 ) 2 MMe +, (Cp)(NPR 3 )MMe +, (Cp)(NCR 2 )MMe +, (Cp)(SiMe 2 NR)MMe +, and (Cp)(OSiR 3 )MMe + . With M = Ti and Zr, the results show that aryl group transfer is more facile for zirconium catalysts than for the corresponding titanium systems. Furthermore, electron-donating ligands and sterically demanding substituents play a crucial role in preventing the aryl transfer reaction. The aryl group transfer is likely to take place for (Cp)(NCR 2 )MMe + with both titanium- and zirconium-ketimide complexes at about 100 °C. However, the decomposition temperature is raised to 250 °C for the corresponding (Cp*)(NCR 2 )TiMe + system.
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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 | 0.001 | 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".