Lactide polymerization catalyzed by Mg and Zn diketiminate complexes with flexible ligand frameworks
Bibliographic record
Abstract
Diketimine ligands bearing N-benzyl, N-9-anthrylmethyl and N-mesitylmethyl substituents (nacnac(Bn)H, nacnac(An)H, and nacnac(Mes)H) were prepared from condensation of the amine with either acetyl acetone or its ethylene glycol monoketal. Chlorination with N-chlorosuccinimide in the 3-position yielded Clnacnac(Bn)H and Clnacnac(An)H. The ligands were reacted with Zn(TMSA)2 (TMSA = N(SiMe3)2) to yield nacnac(An)Zn(TMSA) and Clnacnac(Bn)Zn(TMSA). Protonation with isopropanol afforded nacnac(An)ZnOiPr and Clnacnac(Bn)ZnOiPr. Reaction of the diketimines with Mg(TMSA)2 afforded nacnac(An)Mg(TMSA), nacnac(Mes)Mg(TMSA), Clnacnac(Bn)Mg(TMSA) and Clnacnac(An)Mg(TMSA). Subsequent protonation with tert-butanol produced nacnac(Mes)MgOtBu and Clnacnac(Bn)MgOtBu, but only decomposition was observed with N-anthrylmethyl substituents. Most complexes were characterized by X-ray diffraction studies. TMSA complexes were monomeric and alkoxide complexes dimeric in the solid state. All alkoxide complexes, as well as nacnac(An)Mg(TMSA)/BnOH and Clnacnac(An)Mg(TMSA)/BnOH were moderately to highly active in rac-lactide polymerization (90% conversion in 30 s to 3 h). nacnac(An)ZnOiPr produced highly heterotactic polymers (P(r) = 0.90), Clnacnac(Bn)MgOtBu/BnOH produced slightly isotactic polymers at -30 °C (P(r) = 0.43), and all other catalysts produced atactic polymers with a slight heterotactic bias.
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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 | 0.000 | 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 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".