Reaction of bis(dialkylphosphino)amines R<sub>2</sub>PNHPR<sub>2</sub> (R = <i>i</i>-Pr, <i>t</i>-Bu, Ph) with halogens X<sub>2</sub> (X = Cl, Br, I): different solvents – different stories
Bibliographic record
Abstract
The bis(dialkylphosphino)amines R 2 PNHPR 2 react with elemental halogens X 2 in dichloromethane to produce cationic products of the general form [(R) 2 P(X)-N-(R) 2 P(X)] + (R = i-Pr, Ph, and t-Bu; X = Cl, Br, and I). All of the nine possible products have been isolated and characterized using X-ray diffraction. The dichloro compounds crystallize as [HCl 2 ] − salts, while the dibromo and diiodo products have been isolated as trihalides, [X 3 ] − . A number of these compounds have been shown to react further with methanol to produce salts containing [(R) 2 P(OCH 3 )N(R) 2 P(OCH 3 )] + cations, some of which have also been characterized using X-ray crystallography. The conversion of [(Ph) 2 P(I)-N-(Ph) 2 P(I)][I 3 ] to [(Ph) 2 P(OCH 3 )-N-(Ph) 2 P(OCH 3 )][I 3 ] was monitored using 31 P NMR spectroscopy that revealed a stepwise reaction of the former compound with methanol. The results are discussed within the context of coupled reactions; this is then used to rationalize a mechanism for the formation of a rare catenated bismuth compound we reported previously. We suggest that the formation of the weak Bi–Bi bonds is offset by a coupled or a connected reaction mechanism , involving an irreversible reaction forming strong P–OR bonds in another of the isolated products.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.002 |
| Insufficient payload (model declined to judge) | 0.001 | 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".