Intramolecular C−H and N−H Transfer by Ruthenium(II) Amidophosphine Complexes
Bibliographic record
Abstract
The formation of ruthenium amidophosphine complexes was accomplished by the addition of [P 2 N 2 ]Li 2 (Diox) (where P 2 N 2 is PhP(CH 2 SiMe 2 NSiMe 2 CH 2 ) 2 PPh and Diox is 1,4-dioxane) to [RuCl 2 (cod)] x to generate [P 2 N 2 ]Ru(cod), or to RuCl 2 (PPh 3 ) 3 to generate [P 2 NNH]Ru(C 6 H 4 PPh 2 ). In the former complex, the Ru(II) center is in an octahedral environment perched above the P 2 N 2 macrocycle having two formally anionic amido donors; in the latter complex, there is only one amido ligand with the other as an amine donor where the proton originates from the cyclometalated triphenylphosphine group. Reaction of the tridentate amidophosphine ligand precursor [NPN]Li 2 (THF) 2 (where NPN is PhP(CH 2 SiMe 2 NPh) 2 ) with [RuCl 2 (cod)] x results in the formation of two diastereomeric complexes of the formula [NPNH]Ru(η 3:η 2 -C 8 H 11 ), wherein the cyclooctadiene ligand has been deprotonated by the ancillary ligand to generate a cyclooctadienyl unit. These Ru(II) complexes are five-coordinate with a bidentate PN ligand and a dangling amine unit. The diastereomers are in equilibrium, as shown by variable-temperature NMR studies. The fluxional process that interconverts diastereomers involves proton transfer from the dangling amine arm to the amido unit, a process that equilibrates the two ends of the tridentate NPN ligand on the chemical time scale. Deprotonation of the amine arm by MN(SiMe 3 ) 2 generates a series of ruthenate complexes of the formula [M(THF)]([NPN]Ru(η 3:η 2 -C 8 H 11 )), where M = Li or Na. Addition of Me 3 SiCl results in the formation of new diastereomers that contain silylated dangling arms, and these diastereomers do not interconvert.
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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) | 0.000 | 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) | 0.006 | 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".