(Keynote) Electroreduction of Nitrocyclopropanes and Nitrophenyl Cyclopropanes: Mechanism of Cleavage of the Radical Anion
Bibliographic record
Abstract
There are three possible mechanisms of cleavage of a nitrocyclopropane radical anion 1•‾ , mechanisms A (homolytic cleavage to a cyclopropyl radical 2 • and a nitrite anion), B (homolytic cleavage to a distonic radical anion 3 •‾ ), and C (heterolytic cleavage to a distonic radical anion 4 •‾ [1]. With the models synthesized so far (Y = Z= alkyl, H = COOCH 3 ), only products of mechanism A have been observed [1]. On the other hand, only two cleavage mechanisms are possible for a nitrophenyl cyclopropane radical anion 5 •‾, mechanisms D (homolytic cleavage to the distonic radical anion 6 •‾ ) and E (heterolytic cleavage to the distonic radical anion 7 •‾ ) [1]. The isolation and characterization of the products resulting from the cleavage of the nitrophenyl radical anion 5 •‾ do not allow to distinguish between the two cleavage mechanisms D (homolytic cleavage) and E (heterolytic cleavage) leading to the distonic radical anions 6 •‾ and 7 •‾ respectively. To shed light on the mechanisms of cleavage of those radical anions, density functional (DFT) quantum chemical calculations were carried out on species 1-3 (B3LYP 6-31+G(d), including solvation energies in acetonitrile computed using the polarizable continuum method. The results clearly favor mechanism B and species 3 over mechanisms A and C for the decomposition of anion radicals 1•‾ whenZ = Y = alkyl and X = H . [1] F. Couture-Martin, A. Sardashti, C. Cristea, J.M. Chapuzet, J. Lessard, ECS Transactions , 2008 , 13 , 13-19. Figure 1
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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) | 0.000 | 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) | 0.000 | 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 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".