Substituent Effects on the Thermal Cis-to-Trans Isomerization of 1,3-Diphenyltriazenes in Aqueous Solution
Bibliographic record
Abstract
The thermal cis-to-trans isomerization of some symmetrically p,p'-disubstituted 1,3-diphenyltriazenes has been studied by means of laser-flash photolysis techniques. The geometric isomerization is catalyzed by general acids and general bases as a result of acid/base-promoted 1,3-prototropic rearrangements. Acid catalysis becomes more prominent as the electron-donating character of the para substituent increases, while base catalysis becomes more important as the electron-withdrawing character of the para substituent increases. In addition, the rate ascribed to the interconversion of neutral cis rotamers through hindered rotation around the nitrogen-nitrogen single bond is found to decrease as the electron-withdrawing character of the para substituent increases. Rates of interconversion of neutral cis rotamers are also found to decrease with decreasing solvent polarity, which is indicative of the involvement of a polar transition state. On the other hand, kinetic investigations of the acid-catalyzed decomposition of target triazenes are consistent with an A1 mechanism.
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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 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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 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".