Pyridinium methylide intermediates stabilized by ambiphilic iminophosphorano substituents
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Bibliographic record
Abstract
The previously reported formation of iminophosphorano-substituted bispyridinylidenes 2RR′ from the deprotonation of the related pyridinium salts 1RR′ proceeds through an intermediate that can be detected by NMR spectroscopy. We now show that the NMR spectra are indicative of the formation of a pyridinium ylide intermediate (4RR′), and not the isomeric pyridinylidene (3RR′). Theoretical studies support that the unusual ylide, which features no electron-withdrawing groups on the ylidic carbon, is stabilized by an intramolecular C ylide →P interaction. This interaction also stabilizes the singlet state of the ylide, dampens its nucleophilicity, and demonstrates ambiphilic behaviour of the iminophosphorano substituent (N-donor/P-acceptor).
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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 | 0.000 |
| 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) | 0.002 | 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 it