The role of a hydroxycyclopentadienyl ruthenium dicarbonyl formate in formic acid reductions of carbonyl compounds catalyzed by Shvo's diruthenium catalyst
Bibliographic record
Abstract
Addition of excess HCO 2 H to {2,5-Ph 2 -3,4-Tol 2 (η 5 -C 4 CO)]Ru(CO) 2 } 2 (6) at -20°C led to the formation of [2,5-Ph 2 -3,4-Tol 2 (η 5 -C 4 COH)]Ru(CO) 2 (η 1 -OCHO) (5), a proposed intermediate in catalytic transfer hydrogenations developed by Shvo. Hydroxycyclopentadienyl formate 5 undergoes rapid reversible dissociation of HCO 2 H at 20°C, and undergoes decarboxylation at 1°C to form a 1:10 mixture of {[2,5-Ph 2 -3,4-Tol 2 (η 5 -C 4 CO)] 2 H}Ru 2 (CO) 4 (µ-H) (3):[2,5-Ph 2 -3,4-Tol 2 (η 5 -C 4 COH)Ru(CO) 2 H] (4). 5 does not reduce PhCHO below the temperature at which 5 is converted to hydride 4. The catalytic production of benzyl alcohol from 5 and PhCHO in the presence of excess HCO 2 H is not accelerated by higher concentrations of PhCHO, indicating that 5 does not directly reduce PhCHO. Formate complex 5 is the precursor of hydride 4 which transfers hydrogen to PhCHO. A crucial role for the CpOH proton in the decarboxylation of 5 was indicated by the much slower decarboxylation of the methoxycyclopentadienyl analog [2,5-Ph 2 -3,4-Tol 2 (η 5 -C 4 COCH 3 )]Ru(CO) 2 (η 1 -OCHO) (7). A mechanism for decarboxylation of 5 is proposed which involves reversible dissociation of formic acid to form the unsaturated dienone dicarbonyl ruthenium intermediate C, followed by simultaneous transfer of hydride to ruthenium from the formic acid carbon and of proton to the carbonyl of C from the formic acid OH group.Key words: Shvo catalyst, ruthenium formate, decarboxylation.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| 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; a candidate call from one teacher head, 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".