Radical/Ion Pair Formation in the Electrochemical Reduction of Arene Sulfenyl Chlorides
Bibliographic record
Abstract
Important aspects of the electrochemical reduction of a series of substituted arene sulfenyl chlorides are investigated. A striking change is observed in the reductive cleavage mechanism as a function of the substituent on the aryl ring of the arene sulfenyl chloride. With p-substituted phenyl chlorides a "sticky" dissociative ET mechanism takes place where a concerted ET mechanism leads to the formation of a radical/anion cluster before decomposition. With o-nitropheyl sulfenyl substituted chlorides a stepwise mechanism is observed where through space S...O interactions play an important role stabilizing both the neutral molecules and their reduced forms. Disulfides are generated through a nucleophilic reaction of the two-electron reduction produced anion (arenethiolate) on the parent molecule. The dissociative electron transfer theory, as well as its extension to the case of strong in-cage interactions between the produced fragments, along with the gas phase chemical quantum calculations results helped rationalize both the observed change in the ET mechanism and the occurrence of the "sticky dissociative" ET mechanism. The radical/anion pair interactions have been determined both in solution as well as in gas phase. This study shows that despite the low magnitude of in-cage interactions in acetonitrile as compared to in the gas phase, their existence strongly affects the kinetics of the involved reactions. It also shows that, as expected, these interactions are reinforced by the existence of strong electron-withdrawing substituents.
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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) | 0.001 | 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 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".