Multifunctional Ruthenium Catalysts: A Novel Borohydride-Stabilized Polyhydride Complex Containing the Basic, Chelating Diphosphine 1,4-Bis(dicyclohexylphosphino)butane and Its Application to Hydrogenation and Murai Catalysis
Bibliographic record
Abstract
[RuCl 2 (dcypb)(CO)] 2 2 (dcypb = 1,4-bis(dicyclohexylphosphino)butane) was prepared in high yield via phosphine exchange between dcypb and RuCl 2 (CO)(PPh 3 ) 2 (DMF) ( 1 ). Reaction of 2 with 8 equiv of KBH s Bu 3 affords [ fac -RuH 3 (CO)(dcypb)] - ( 3 ), stabilized by interactions with a K + counterion and an intact KBH s Bu 3 molecule in the third coordination sphere. Substantial ion pairing accounts for the stability and high hydrocarbon solubility of 3 . Complex 3 effects reduction of benzophenone under unprecedentedly mild conditions, at 1 atm of H 2 in refluxing 2-propanol. It is also active for ortho functionalization of benzophenone under 20 atm of ethylene. Stoichiometric experiments reveal facile formation of ortho-metalated RuH(CO)[OC(C 6 H 4 )(Ph)](dcypb) ( 5 ), an intermediate proposed in both types of catalysis. The catalytic activity of isolated 5 supports this hypothesis in the case of hydrogenation but not of Murai catalysis. The X-ray crystal structures of 3 and 5 are reported.
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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 | 0.000 |
| 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 | 0.001 | 0.000 |
| Research integrity | 0.001 | 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".