Computational design of ruthenium hydride olefin-hydrogenation catalysts containing hemilabile ligands<sup>,</sup>
Bibliographic record
Abstract
Three ruthenium hydridocarbonyl complexes containing bidentate hemilabile ligands have been evaluated as possible catalysts for the H2 hydrogenation of olefins. Our previous investigations of the mainstay hydridoruthenium catalyst, RuHCl(CO)(PR3)2 (1), indicated that the rate-limiting olefin-insertion barrier was increased by the need for an H2 molecule to act as a stabilizing two-electron donor. Using density functional theory (DFT) calculations, we have determined that a P,N phosphane-oxazoline would be suitable for stabilizing the metal center of the complex RuHCl(CO)(PiPr3)(DZ), where DZ is a neutral bidentate hemilable ligand. In the reaction catalyzed by this complex, the olefin insertion occurs before the coordination of H2, avoiding the entropic penalty of coordinating H2. We predict that the phosphane-oxazoline containing catalyst will have higher activity than 1 and a different rate-law, zero-order in [H2]. The oxazoline increases the strength of coordination of the ethylene due to stronger back-donation from destabilized Ru d-orbitals to the ethylene π* molecular orbital.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.001 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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".