Termination and Transfer Reactions in the Group Transfer Polymerizations of Acrylates Catalyzed by Mononuclear Early d-Block and f-Block Metallocenes: A DFT Study
Bibliographic record
Abstract
The group transfer polymerization (GTP) of acrylates with early d-block and f-block metallocenium ester enolates suffers from side reactions, which cause the process not to be living, with a lack of control of the number-average molecular weight, molecular weight distribution, and tacticity, as well as an incomplete monomer conversion at low catalyst loadings. GTP of acrylates has so far met with limited success, due to the presence of a proton on the α-carbon, which provides low steric protection to the enolate in the unwanted backbiting reaction. Furthermore, the proton on the α-carbon is relatively acidic and therefore can be transferred. The computational study with the BP86 DFT functional of the backbiting and proton transfer reactions on realistic models for acrylate GTP provides detailed information on the mechanisms and hints on how to tailor the existing catalysts in order to minimize the unwanted side reactions.
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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 | 0.001 | 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 | 0.000 | 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 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".