The life, death, and ROMP activity of ruthenium complexes containing the basic, chelating diphosphine bis(dicyclohexyl)-1,4-phosphinobutane
Bibliographic record
Abstract
Reaction of RuCl 2 (PPh 3 ) 3 with bis(dicyclohexyl)-1,4-phosphinobutane (dcypb) under N 2 affords access to a formerly elusive family of dcypb complexes based on the RuCl 2 (PP) core. Under Ar or vacuum atmosphere, decomposition occurs via Ru-promoted dehydrogenation of the dcypb ligand. While the N 2 -stabilized species [RuCl 2 (dcypb)] 2 (N 2 ) (4a) is easily handled under N 2 in nonchlorinated solvents, reaction with chlorinated solvents rapidly yields paramagnetic Ru 2 Cl 5 (dcypb) 2 (5). The N 2 ligand within 4a is readily displaced under H 2 or CO atmosphere, yielding Ru 2 Cl 4 (dcypb) 2 (H 2 ) (6) or RuCl 2 (dcypb)(CO) 2 , the latter as a mixture of ccc-(7) and tcc-(8) isomers. Benzylidene derivative RuCl 2 (dcypb)(CHPh) (1a), prepared in situ by reaction of 4a with PhCHN 2 , proves exceptionally active in ring-opening metathesis polymerization (ROMP) of norbornene. The X-ray crystal structure of 5 is reported: triclinic, a = 13.390(2), b = 15.726(2), c = 19.524(2) Å, α = 77.325(2), β = 70.964(2), γ = 73.478(2)°, with space group P[Formula: see text] and Z = 2.Key words: ruthenium, alkylphosphine, dehydrogenation, carbene, metathesis, crystal structure.
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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 | 0.001 | 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 | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".