TEMPS, the Chalcogen Cousin of the Infamous Stable Radical TEMPO, Traps Radicals via Substitution on Its Dimer (TEMPS)<sub>2</sub>
Bibliographic record
Abstract
Abstract Nitroxides such as 2,2,6,6‐tetramethylpiperidin‐N‐oxyl (TEMPO) are the quintessential organic radicals. They are commonly used to trap alkyl radicals in controlled radical polymerizations, synthetic transformations and mechanistic experiments, and peroxyl radicals when applied as radical‐trapping antioxidants (RTAs). Relatively little is known about their sulfur analogs (N‐thiyl radicals, R2NS• and dithiobisamines, R2NS‐SNR2). We found that dithiobisamines of moderate steric bulk (including (TEMPS)2, the dimer of the sulfur analog of TEMPO), trapped peroxyl radicals with rate constants up to 1.2 × 106 m−1s−1 (at 100 °C) – similar to TEMPO. Unlike TEMPO, their radical‐trapping activity was not catalytic, independent of the rate of radical initiation and still operative in saturated hydrocarbons – implying a distinct mechanism. Additional experimental data and computations point to a homolytic substitution mechanism, analogous to that recently elucidated for tetrasulfides. In the absence of O2, alkyl radicals and dithiobisamines react to form sulfenamides, which may be exploited for synthetic purposes.
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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 | 0.001 |
| 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 | 0.001 |
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".