A Diruthenium μ<i>-</i>Methylene Complex
Bibliographic record
Abstract
The reaction of [Ru 2 (μ-CO)(CO) 4 (μ-dppm) 2 ] ( 1; dppm = Ph 2 PCH 2 PPh 2 ) with CH 2 N 2 gives the μ -methylene complex [Ru 2 ( μ -CH 2 )(CO) 4 (μ-dppm) 2 ] ( 2 ), and complex 2 reacts with CO to regenerate complex 1 with loss of ketene. Complex 2 reacts with HBF 4 or CF 3 SO 3 H at low temperature to form the fluxional μ-methyl complex [Ru 2 (μ-CH 3 )(CO) 4 (μ-dppm) 2 ] + ( 3 ). Variable-temperature 1 H, 13 C, and 31 P NMR studies establish that the μ-CH 3 group has an unsymmetrical coordination mode with an agostic hydrogen and is fluxional. At room temperature, the reaction of 2 with formic acid gives an equimolar mixture of complex 1 and [Ru 2 (μ-H)(H)(μ-CO)(CO) 2 (μ-dppm) 2 ] ( 4 ), which is an active catalyst for the decomposition of formic acid to hydrogen and carbon dioxide, and the reaction is shown to occur via the intermediate complexes 3 and [Ru 2 (μ-H){μ-C(O)Me}(HCOO)(CO) 3 (μ-dppm) 2 ] + ( 5 ). The reaction of 2 with acetic acid at room temperature gives in sequence the complexes [Ru 2 {μ-C(O)Me}(OAc)(CO) 3 (μ-dppm) 2 ] ( 6 ) and [Ru 2 (μ-H){μ-C(O)Me}(OAc)(CO) 3 (μ-dppm) 2 ] + ( 7 ) before loss of methane occurs with formation of [Ru 2 (μ-OAc)(CO) 4 (μ-dppm) 2 ] + ( 8 ). Complex 2 reacts with methyl triflate to give ethylene and [Ru 2 (μ-H)(μ-CO)(CO) 3 (μ-dppm) 2 ] + ( 9 ), as the triflate salt, probably via an intermediate with an ethylruthenium group. In the presence of HBF 4, complex 2 is an efficient precatalyst for the ring-opening polymerization of norbornene.
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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) | 0.000 | 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) | 0.074 | 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 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".