Synthesis of <i>c</i><i>yclo</i>-2,4,6-Triarsa-1,3,5-triazanes from <i>c</i><i>yclo</i>-2,4-Diarsa-1,3-diazanes Demonstrating the General Influence of Substituent Steric Strain on the Relative Stability of Pnictazane Oligomers
Bibliographic record
Abstract
2,4-Dichloro-1,3-diaryl-cyclo-2,4-diarsa-1,3-diazanes (aryl = 2,6-dimethylphenyl, Dmp, or 2,6-diisopropylphenyl, Dipp) have been transformed into the corresponding 2,4,6-trichloro-cyclo-2,4,6-triarsa-1,3,5-triazanes on reaction with GaCl(3) followed by 4-(dimethylamino)pyridine (DMAP). The nitrogen bound Dmp and Dipp substituents impose "medium" substituent steric strain on the heterocycles influencing the relative thermodynamic stability of potential oligomers in favor of the trimers. This ring expansion disproportionation reaction is initiated by chloride ion abstraction, and the intermediate 2,4-dichloro-1,3,5-tris(2,6-diisopropylphenyl)-cyclo-2,4-diarsa-1,3,5-triazane-6-arsenium tetrachlorogallate has been isolated and structurally characterized. Subsequent reaction with 4-(dimethylamino)pyridine (DMAP) effects release of chloride ion from the gallate anion and consequential formation of a covalent As-Cl bond in the trimer. The observations are analogous to those for the phosphorus derivatives demonstrating a general applicability of this new synthetic procedure for the development and diversification of cyclopnictazane chemistry.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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 source (direct Gemma or distilled Codex), 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".