Regioselective SO vs. CO bond cleavage in sulfenate ester radical anions
Bibliographic record
Abstract
The electron transfer (ET) reduction of benzyl benzenesulfenate ester (1) and tert-butyl benzenesulfenate ester (2) was investigated using electrochemical techniques. Analysis of the cyclic voltammetry of each compound suggests that the ET reduction proceeds via a stepwise dissociative mechanism. The voltammograms of 1 are similar to those of diaryl disulfides and it was found through controlled potential electrolysis (CPE) product studies that ET reduction leads to SO bond cleavage. The voltammograms of 2 are dramatically different with a sharper dissociative wave occurring at a more negative peak potential. CPE experiments indicate products that result from ET leading to CO bond cleavage in this case. DFT calculations of the singly occupied molecular orbitals (SOMOs) of 1 and 2 were performed and offer a rationale for the different reactivity of the two radical anions.Key words: sulfenate esters, dissociative electron transfer, electrochemistry, radical anions.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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".