Diverse Reactivity of the<i>cyclo</i>-Diphosphinophosphonium Cation [(P<i>t</i>Bu)<sub>3</sub>Me]<sup>+</sup>: Parallels with Epoxides and New<i>catena</i>-Phosphorus Frameworks
Bibliographic record
Abstract
The cyclo-diphosphinophosphonium salt [(PtBu)3Me][OTf] (2) has been shown to be highly reactive toward Lewis bases, exhibiting diverse reactivity with phosphines, 4-(dimethylamino)pyridine (dmap) and chlorophosphines, providing approaches to new open-chain and cyclic catena-phosphorus frameworks. Reaction of 2 with R3P (R = Me or nPr) or dmap led to the ring-opened adducts [R3P-PtBu-PtBu-P(Me)tBu][OTf] (R = Me (4a), nPr (4b)) and [(dmap)-PtBu-PtBu-P(Me)tBu][OTf] (6), respectively. The complicated (31)P{(1)H} NMR spectra of the three compounds were simulated, evidencing the presence of two diastereomeric forms of 4a, and single diastereomers of 4b and 6. This ring-opening reactivity of the cation in 2 parallels the reactivity of isolobal epoxides with nucleophiles under acidic conditions. Compound 2 was also shown to react with a 2:1 mixture of Me2PCl and TMSOTf to form the unexpected cyclo-diphosphino-1,2-diphosphonium salt [(Me2P)2(PtBu)2][OTf]2 (8), which is postulated to result from two consecutive ring-opening and ring-closing steps. In contrast, reaction with MePCl2 furnished [(MeP)(PtBu)2(P(Me)tBu)][OTf] (9), consistent with insertion of a "MeP" moiety into the cationic phosphorus framework of 2. The importance of ring strain on the reactivity of the cation in 2 was illustrated by comparative studies of the corresponding cyclo-tetraphosphorus cation in [(PtBu)4Me][OTf] (10), which exhibits no reactivity under analogous conditions.
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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 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 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".