ESI-MS Insights into Acceptorless Dehydrogenative Coupling of Alcohols
Bibliographic record
Abstract
High Resolution Image Download MS PowerPoint Slide Acceptorless dehydrogenative coupling (ADC) reactions catalyzed by a series of Ru and Os complexes were studied by ESI-MS. Important ethoxo, 1-ethoxyethanolate, and hydride intermediates were intercepted in the ADC of ethanol to ethyl acetate. Collision-induced dissociation (CID) experiments were applied as a structure elucidation tool and as a probe of the propensity of the reaction intermediates to evolve acetaldehyde, ethyl acetate, and H 2, relevant to the catalytic cycle. The key mechanistic step producing ethyl acetate from the 1-ethoxyethanolate intermediates was documented. Energy-dependent CID experiments demonstrated the importance of a vacant coordination site for efficient production of ethyl acetate. The versatility and potential broad applicability of ESI-MS and its tandem version with CID was further illustrated for the ADC reaction of alcohols with amines, affording amides. A mechanism related to that found for the ester synthesis is plausible, with the key step involving formation of a hemiaminaloxide intermediate.
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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) | 0.002 | 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".