Inhibiting σ → π Isomerization of Aryloxide Ligands in Late Transition-Metal Complexes
Bibliographic record
Abstract
The room-temperature reaction of thallium perfluorophenoxide with RuHCl(PPh 3 ) 3 ( 4a ) yields RuH(σ-OC 6 X 5 )(PPh 3 ) 3 (X = F, 5 F ), the structure of which was confirmed by spectroscopic, microanalytical, and X-ray analysis. The analogous phenoxide complex (X = H, 5 H ) is known to be unstable toward σ → π isomerization, and reaction of phenoxide ion with 4a affords RuH(η 5 -C 6 H 5 O)(PPh 3 ) 2 ( 6a ). We conclude that the driving force for isomerization in 5 F is minimized by the electron deficiency of the perfluorophenoxide ring. In contrast, incorporation of the aryloxide entity within a chelating framework proves insufficient to inhibit isomerization. Thus, reaction of 4a or RuCl 2 (PPh 3 ) 3 ( 4b ) with the sodium salt of 2‘-(diphenylphosphino)-1,1‘-binaphthyl-2-ol (NaO-MOP) yields RuX(O-MOP)(PPh 3 ) ( 7a, X = H; 7b, X = Cl). Detailed 1- and 2-D NMR analysis of 7b provides unequivocal evidence that the O-MOP ligand is bound to Ru in a σ fashion through phosphorus and in a π fashion via the aryloxide ring. The crystal structure of 5 F ·THF is reported.
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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 | 0.001 |
| 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) | 0.008 | 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".