Possible Thermal Decomposition Routes in [MeB(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>]<sup>-</sup>[L<sub>2</sub>TiMe<sup>+</sup>] as Deactivation Pathways in Olefin Polymerization Catalysis: A Combined Density Functional Theory and Molecular Mechanics Investigation
Bibliographic record
Abstract
Combined quantum mechanical (QM) and molecular mechanical (MM) models (QM/MM) have been used to explore possible decomposition routes for ion pair systems used as catalysts in olefin polymerization. The catalyst systems include [MeB(C 6 F 5 ) 3 ] - [(NPR 3 ) 2 TiMe + ], [MeB(C 6 F 5 ) 3 ] - [(Cp)(NCR 2 )TiMe + ], and [MeB(C 6 F 5 ) 3 ] - [(Cp)(SiMe 2 NR)TiMe + ]. The possible thermal decomposition routes for the above catalyst systems include fluorine transfer from [MeB(C 6 F 5 ) 3 ] - to the metal center, aryl transfer (C 6 F 5 ) to the growing chain, transfer of B(C 6 F 5 ) 3 from [MeB(C 6 F 5 ) 3 ] - to the ancillary ligand, exchange of methyl on butyl from the ancillary ligand with aryl in [MeB(C 6 F 5 ) 3 ] -, transfer of hydrogen from the Cp* ring to the growing chain, and transfer of hydrogen from the methyl group on tertiary butyl to the growing chain. The activation barriers fall in the range 15.5−68.7 kcal/mol. The transfer of fluorine from the counterion to the metal center is the most facile deactivation pathway.
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 | 0.002 | 0.001 |
| Meta-epidemiology (narrow) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.002 | 0.003 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| 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".