Palladium(II) Complexes of 1‐Phosphaisoprene Molecules and Polymers: Reversible Cross‐Linking of a Phosphorus‐Containing Polymer
Bibliographic record
Abstract
Abstract The anionic polymerization of 1‐phosphaisoprene [Mes*P=C(Me)−CH=CH2 (E‐1)] affords poly(1‐phosphaisoprene) 2 in high yield (75 %). Concentrated solutions of polymer 2 (Mn=21,800 g mol−1; Đ=1.02) a P‐analogue of natural rubber, undergo gelation upon treatment with [Pd(cod)Cl2] (0.15 P equiv). Evidence for P‐coordination of 2 to PdII was obtained by 31P and 1H NMR spectroscopy. The gelation is reversed by the addition of PMe3 and the reformation of recoverable 2 along with [PdII−PMe3] complexes were confirmed by 31P NMR spectroscopy. The use of labile metal‐ligand bonds to reversibly form gels is unprecedented and has relevance to self‐healing materials. In contrast, coordination of 2 to [Pd(η3‐C3H5)(μ‐Cl)]2 affords the well‐defined complex 2 ⋅ [Pd(η3‐C3H5)Cl] which was characterized by 31P, 1H, 13C{1H} NMR spectroscopy and GPC. This polymer chemistry was complemented by detailed molecular model studies of the coordination chemistry of monomer 1‐phosphaisoprene E‐1 with [Pd(cod)Cl2] and [Pd(η3‐C3H5)(μ‐Cl)]2].
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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) | 0.002 | 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".