Transition Metal-Induced Cyclization of 1-Phosphabutadienes: Selective Formation of 1-Phosphet-2-ene or P═C-Substituted Phosphacyclohexene Ligands
Bibliographic record
Abstract
The cycloaddition of 1-phosphabutadienes with AuI and PdII proceeds very differently when the hydrogen substituent in the 3-position is replaced by methyl. Specifically, 1-phosphaisoprene [Mes*P═C(Me)─CH═CH2, E-1a] was treated with [Au(tht)Cl] (tht = tetrahydrothiophene) to afford a phosphaalkene-substituted phosphacyclohexene binuclear AuCl complex. This intermolecular [4 + 2] cycloaddition is analogous to the Diels–Alder reaction and proceeds via the end-on complex [Au(E-1a)Cl], which was also isolated. In contrast, the reaction of 1-phosphabutadiene Mes*P═C(Me)─C(Me)═CH2 (E-1b) with [Au(tht)Cl] selectively afforded the 1-phosphet-2-ene-AuI complex [CH2─C(Me)═C(Me)─P(Mes*)AuCl] in near quantitative conversion. This intramolecular [2 + 2] cycloaddition also occurred when E-1b was reacted with [Pd(η3-C3H5)(μ-Cl)]2 or [Pd(cod)Cl2] (COD = cyclooctadiene) to afford complexes [CH2─C(Me)═C(Me)─P(Mes*)Pd(η3-C3H5)Cl] and [(CH2─C(Me)═C(Me)─P(Mes*))2PdCl2], respectively. All the complexes were fully characterized spectroscopically and structurally.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.002 |
| 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 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".