New Synthetic Procedures to <i>Catena</i>-Phosphorus Cations: Preparation and Dissociation of the First <i>cyclo</i>-Phosphino-halophosphonium Salts
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Bibliographic record
Abstract
Chlorination of 1,2,3,4-tetracyclohexyl-cyclo-tetraphosphine (2) by PhICl(2) or PCl(5) in the presence of Me(3)SiOTf or GaCl(3) provides a stepwise approach to salts of the first cyclo-phosphino-chlorophosphonium cations [Cy(4)P(4)Cl](+) ([19](+)) and [Cy(4)P(4)Cl(2)](2+) ([20](2+)). The analogous iodo derivative [Cy(4)P(4)I](+) ([17](+)) is obtained as the tetraiodogallate salt from reaction of 2 with I(2) in the presence of GaI(3). Reactions of the dication [20](2+) with PMe(3) or dmpe effect a dissociation of the cyclic framework resulting in the formation of salts containing [Me(3)PPCyPCyPMe(3)](2+) ([27](2+)), [dmpeCyP](2+) ([29](2+)), and [dmpeCyPCyP](2+) ([30](2+)), respectively. The new cations represent phosphine complexes of the [PCy](2+) and [P(2)Cy(2)](2+) cationic fragments from [20](2+), demonstrating the coordinate nature of the phosphinophosphonium bonds in cyclo-phosphino-halophosphonium cations. The compounds have been characterized by NMR spectroscopy, single crystal X-ray crystallography, and Raman spectroscopy.
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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 | 0.001 |
| 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 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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 it