Hydrogenation of carbon dioxide catalyzed by ruthenium trimethylphosphine complexes Effect of gas pressure and additives on rate in the liquid phase
Bibliographic record
Abstract
Kinetic and mechanistic studies of CO2 hydrogenation were performed in liquid triethylamine and at subcritical CO2 pressures to avoid complications from phase behaviour that are observed under supercritical conditions. Kinetic measurements of the hydrogenation of CO2 to formic acid, catalyzed by RuCl(O2CMe)(PMe3)4, support a CO2 insertion mechanism. The reaction is first-order in both H2 and CO2 under most conditions. The rate is strongly dependent on the choice of additive, with methanol giving the greatest rates. Because only trace amounts of methanol are needed, the effect of the additive is believed to involve direct interactions with the catalyst rather than changes in the physical properties of the reaction medium. The optimized rates exceed 3500 h1. Addition of an inert gas affects the rate of the reaction, probably via the phenomenon of gas expansion of the liquid phase.Key words: carbon dioxide, homogeneous catalysis, hydrogenation, formic acid, expanded liquids.
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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 | 0.001 |
| 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) | 0.001 | 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".