Comparison of the Catalytic Activity of [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Ru(2,2′-bipyridine)(L)]OTf versus [(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Ru(6,6′-diamino-2,2′-bipyridine)(L)]OTf (L = labile ligand) in the Hydrogenation of Cyclohexanone. Evidence for the Presence of a Metal–Ligand Bifunctional Mechanism under Acidic Conditions
Bibliographic record
Abstract
The two title complexes as well as the dimeric complex [Ru(II)(η 5 -C 5 H 5 )(6,6′-diamino-2,2′-bipyridine)] 2 (OTf) 2 have been synthesized and characterized by NMR and single-crystal X-ray crystallography. The direct structural comparison of the 2,2′-bipyridine and 6,6′-diamino-2,2′-bipyridine complexes suggests that the electronic and steric environments of the ruthenium centers in both complexes are essentially equivalent, providing for a unique opportunity to probe the influence of the noncoordinated amine substituent on the relative reactivity and catalytic activity of the complexes. Opposite to what would be anticipated on the basis of steric effects, the bulkier amine-substituted ligand results in a catalyst showing substantially higher activity in the hydrogenation of cyclohexanone in acidic medium, which is attributed to the operation of a metal–ligand bifunctional hydrogenation mechanism mediated by the amine substituents in their protonated form acting as proton shuttles.
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How this classification was reachedexpand
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 | 0.003 | 0.005 |
| Meta-epidemiology (narrow) | 0.002 | 0.001 |
| Meta-epidemiology (broad) | 0.003 | 0.002 |
| Bibliometrics | 0.001 | 0.007 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.000 | 0.002 |
| Open science | 0.003 | 0.001 |
| Research integrity | 0.001 | 0.002 |
| 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 itClassification
machine, unvalidatedMachine predicted; both teacher heads agree on what is shown here.
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".