Kinetics and mechanism of the oxidation of alcohols by tetrapropylammonium perruthenate
Bibliographic record
Abstract
2-Propanol is oxidized by tetrapropylammonium perruthenate (TPAP) in a reaction that is second order in TPAP and first order in 2-propanol. One of the products, believed to be ruthenium dioxide, is an effective catalyst for the reaction, making it an autocatalytic process. The rate of oxidation is relatively insensitive to the presence of substituents. Primary kinetic deuterium isotope effects are observed when either the hydroxyl or the α hydrogen is replaced by deuterium. The only product obtained from the oxidation of cyclobutanol is cyclobutanone, indicating that the reaction is a two-electron process. Tetrahydrofuran is oxidized at a rate that is several orders of magnitude slower than that observed for 2-propanol, suggesting that the reaction of TPAP with alcohols may be initiated by formation of perruthenate esters. A tentative mechanism consistent with these observations is proposed.Key words: oxidation, alcohols, tetrapropylammonium perruthenate, reaction mechanism, autocatalysis.
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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 | 0.000 |
| 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".