Experimental and Computational Study of Pincer Complexes of Ruthenium with Py, CO, and N<sub>2</sub> Ligands
Bibliographic record
Abstract
Addition of pyridine to the syn and anti isomers of cis -RuHCl[ t Bu 2 PCH 2 CH 2 (( E )-CH CH)CH 2 PBu t 2 ] ( 1 ) afforded a single isomer of trans, cis, anti -RuHCl(Py)[ t Bu 2 PCH 2 CH 2 (( E )-CH CH)CH 2 PBu t 2 ] ( 2 ), where the anti α-HC-RuH configuration was established by a difference NOE experiment. The carbonyl complex RuCl(CO)[CH(C 2 H 4 PBu t 2 ) 2 ] ( 3 ) was obtained from 2 under CO, and two hydride complexes, RuH(CO)[CH(C 2 H 4 PBu t 2 ) 2 ] ( 4 ) and RuH(N 2 )[CH(C 2 H 4 PBu t 2 ) 2 ] ( 5 ), were prepared from 3 and 1, respectively, using Li[HBEt 3 ] as the hydride source. Decarbonylation of isoamyl alcohol with polymeric [RuCl 2 (COD)] n in the presence of 1,5-bis(di- tert -butylphosphino)pentane (D t BPP) resulted in isolation of the 16-atom-ring binuclear species [RuHCl(CO)(D t BPP)] 2 ( 6 ). New products 3 − 5 were characterized by single-crystal X-ray analysis. In the computational study, we successfully modeled complexes 1 − 4 using the ONIOM methodology. It was established that the bulky PBu t 2 groups are responsible for the electronically unfavorable cis arrangement of the CO and Cl ligands in 3 . B3PW91 calculations of the transition state structures for the intramolecular olefin insertion into the Ru−H bond in anti - 1, trans,cis - 2, and cis,trans - 2 gave barrier heights of 28.3, 27.1, and 17.7 kcal/mol, respectively.
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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 | 0.000 |
| 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) | 0.003 | 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".