Models for the Anionic Polymerization of P═C Bonds: Cyclization of <i>n</i> ‐BuLi‐Initiated MesP═CPh <sub>2</sub> and Related Phosphaalkenes with H <sub>2</sub> C═CPh <sub>2</sub>
Bibliographic record
Abstract
Abstract To model the first propagation step in the anionic polymerization of MesP═CPh 2 we studied the addition of Li[MesP(Bu)–CPh 2 ] (and related species) to nonpolymerizable H 2 C═CPh 2 . Addition proceeds via the o ‐CH 3 of the P‐Mes followed by unprecedented cyclization to C 5 P‐rings with release of Li[CHPh 2 ]. Further investigation of the aforementioned reaction using phosphaalkenes, RP═CAr 2 (R ═ Mes, m ‐Xyl; R′ ═ Ph, 4‐FC 6 H 4 , 4‐MeC 6 H 4 , 4‐MeOC 6 H 4 ), resulted in the observation of a relatively long‐lived intermediate in two instances (R ═ Mes, R’ = 4‐MeC 6 H 4 , 4‐MeOC 6 H 4 ). For the latter, the intermediate was identified as n ‐BuP(CH(4‐MeOC 6 H 4 ) 2 )[C 6 (4,6‐Me 2 )H 2 –(2‐CH 2 CH 2 CPh 2 Li) by isolation of the oxidized, H + ‐quenched product. These observations provide intriguing clues into the complex mechanism of polymerization of P ‐Mes phosphaalkenes and the chiral cyclophosphane products are of interest as ligands for catalytic applications.
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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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.003 | 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".