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 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 | 0.003 | 0.002 |
| Meta-epidemiology (narrow) | 0.003 | 0.003 |
| Meta-epidemiology (broad) | 0.004 | 0.002 |
| Bibliometrics | 0.002 | 0.006 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.002 | 0.002 |
| Insufficient payload (model declined to judge) | 0.000 | 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; both teacher heads agree on what is shown here.
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".