First-Principles Quantum Chemical Study of Thermal Decomposition Routes for the Cationic Catalyst L<sub>2</sub>TiMe<sup>+</sup>
Bibliographic record
Abstract
Density functional theory has been used to investigate the various decomposition pathways involving the cationic catalyst systems L 2 TiMe + . The cationic catalyst systems include (NPR 3 ) 2 TiMe +, (Cp)(NPR 3 )TiMe +, (Cp)(NCR 2 )TiMe +, (Cp)(SiMe 2 NR)TiMe +, and (Cp)(OSiR 3 )TiMe + . The possible decomposition routes for the above catalyst systems include transfer of methyl on the butyl group from the ancillary ligand to the metal center, transfer of butyl from the ancillary ligand to the metal center, transfer of hydrogen of methyl on the butyl group from the ancillary ligand to the metal center, and transfer of methyl on Si (this is the case for the constrained-geometry catalyst) to the metal. The activation barriers for the above decomposition reactions fall in the range 16−63 kcal/mol. The transfer of methyl on the butyl group from the ancillary ligand to the metal center is more facile for the constrained-geometry catalyst than the other catalyst systems considered in this study. Furthermore, the transfer of butyl from the ancillary ligand to the metal center is a potential deactivation pathway for (NPR 3 ) 2 TiMe +, (Cp)(NPR 3 )TiMe +, (Cp)(NCR 2 )TiMe +, and (Cp)(OSiR 3 )TiMe + . However, this is not the case for (Cp)(SiMe 2 NR)TiMe + systems. Ring-metalated metallacyclic complexes that result from an intramolecular C−H activation are also potential deactivation pathways for the catalyst systems considered in this study.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.000 | 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; 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".