A Unique Autocatalytic Process and Evidence for a Concerted-Stepwise Mechanism Transition in the Dissociative Electron-Transfer Reduction of Aryl Thiocyanates
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Bibliographic record
Abstract
Electrochemical reduction of p-methyl-, p-methoxy-, and 3,5-dinitrophenyl thiocyanates as well as p-methyl- and p-methoxyphenyl disulfides was investigated in acetonitrile at an inert electrode. This series of compounds reveals a striking change in the reductive cleavage mechanism of the S-CN bond in thiocyanates as a function of the substituent on the aryl ring of the aryl thiocyanate. With nitro substituents, a stepwise mechanism, with an anion radical as the intermediate, takes place. When electron-donating groups (methyl and methoxy) are present, voltammetric as well as convolution analyses provide clear evidence for a transition between the concerted and stepwise mechanisms based on the magnitude of the transfer coefficient alpha. Moreover, a very interesting autocatalytic process is involved during the electrochemical reduction of these compounds. This process involves a nucleophilic substitution reaction on the initial aryl thiocyanate by the electrochemically generated arenethiolate ion. As a result of this unusual process, the electrochemical characteristics (peak potential and peak width) of the investigated series are concentration dependent.
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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 | 0.001 | 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 it