Compatibility of the Vinylidene Ligand and Perfluorophenoxide
Bibliographic record
Abstract
This study demonstrates the stability of the Ru-vinylidene moiety toward installation of a perfluorophenoxide ligand. The room-temperature reaction of RuCl(dcypb)(μ-Cl) 3 Ru(dcypb)(N 2 ) ( 3 ) with TlOC 6 F 5 and excess tert -butylacetylene yields mononuclear Ru(OC 6 F 5 ) 2 (dcypb)( C CHBu t ) ( 6, dcypb = 1,4-bis(dicyclohexylphosphino)butane). Intermediates en route to 6 are the face-bridged dimers RuCl(dcypb)(μ-Cl) 3 Ru(dcypb)( C CHBu t ) ( 4a ) and [{Ru(dcypb)( C CHBu t )} 2 (μ-Cl) 3 ]OC 6 F 5 ( 5 ·OC 6 F 5 ): the cation in the latter was characterized as its PF 6 salt (reaction halting at 5 ·PF 6 on use of TlPF 6 in place of TlOC 6 F 5 ). Edge-bridged, dicationic [{RuCl(dcypb)( C CHBu t )} 2 (μ-Cl) 2 ](OC 6 F 5 ) 2 ( 8 ) is also a probable intermediate in this reaction pathway: although not observed directly, the dication was isolated in low yields as its BAr f 4 salt, on reaction of 5 ·PF 6 with NaBAr f 4 (BAr f 4 - = [B{C 6 H 3 (CF 3 ) 2 -3,5} 4 ] - ). A minor byproduct in the synthesis of 6 is acetylide Tl[{Ru(C⋮CBu t )(dcypb)} 2 (μ-Cl) 3 ] ( 7 ), formed by deprotonation of the vinylidene ligand in 5 ·OC 6 F 5 by TlOC 6 F 5 . (An alternative representation of 7 as a covalent Ru(μ-Cl) 2 Tl species is supported by X-ray evidence, at least in the solid state.) Importantly, the deprotonation reaction is reversible, and competing reprotonation of 7 by the phenol coproduct enables re-formation of 5 ·OC 6 F 5 . Nucleophilic attack by the aryloxide anion on the metal center enables complete and irreversible transformation to 6, illustrating the mutual compatibility of the vinylidene and perfluorophenoxide ligands. As expected from the high thermodynamic stability of the Ru 2 (μ-Cl) 3 entity, complexes 5 ·PF 6 and 5 ·Cl exhibit low activity in ring-opening metathesis polymerization of norbornene. Mononuclear 6, containing four nonlabile ligands cis to the vinylidene moiety, is likewise quite unreactive until activated by protonolysis of aryloxide. Product identities were established by 1 H, 13 C, and 31 P NMR and IR spectroscopy, and ( 6, 7, 8 ) X-ray crystallography.
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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 | 0.001 |
| 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 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".