Phosphenium-Insertion and Chloronium-Addition Reactions Involving the cyclo-Phosphanes (t-BuP)n (n = 3, 4)
Why this work is in the frame
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
The transfer of a Ph2P+-moiety provided by Ph2PCl and chloronium-addition with PCl5 or PhICl2 to the cyclo-phosphanes (t-BuP)n (n = 3 (4), 4 (5)) were investigated. The reactions strongly depend on the presence of GaCl3 or Me3SiOTf as a halide abstracting reagent. The reaction of 4 with Ph2PCl and GaCl3 quantitatively yields cation [Ph2P(t-BuP)3]+ (6+) as a GaCl4–-salt. Using Me3SiOTf as a halide abstracting reagent leads to the ring expansion of (t-BuP)3 (4) to tetrameric (t-BuP)4 (5) and cation 6+ is only formed as a minor product. Chloronium addition employing the PCl5/GaCl3 or PhICl2/Me3SiOTf systems as Cl+-sources to 4 gives complex reaction mixtures. In contrast, the Cl+-addition to 5 gives cation [Cl(t-BuP)4]+ (8+) quantitatively when the system PCl5/GaCl3 is used. Utilising PhICl2 in the presence of Me3SiOTf gives t-BuPCl2 as the main product.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.016 | 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