Benzonitrile Adducts of Terminal Diarylphosphido Complexes: Preparative Sources of “Ru═PR<sub>2</sub>”
Bibliographic record
Abstract
Dehydrohalogenation of secondary diarylphosphine ruthenium complexes in the presence of benzonitrile yields stable, isolable nitrile adducts of the formula [Ru(η 5 -indenyl)(PAr 2 )(NCPh)(PPh 3 )], in which the terminal phosphido ligand is pyramidal at P and contains a stereochemically active lone pair. Unlike the analogous carbonyl adducts [Ru(η 5 -indenyl)(PAr 2 )(CO)(PPh 3 )], these benzonitrile complexes behave as masked sources of the highly reactive planar phosphido complexes [Ru(η 5 -indenyl)(PAr 2 )(PPh 3 )], which contain a Ru═PAr 2 π bond. This is illustrated by the addition (or cycloaddition) reactions of the benzonitrile adducts with dihydrogen, methyl iodide, and 1-hexene, as well as their thermal decomposition via orthometalation of the PPh 3 ligand. Enthalpies of CO vs NCPh dissociation from the [Ru(η 5 -indenyl)(PR 2 )(PPh 3 )] fragments (R = alkyl, aryl) have been calculated, as has the trajectory of addition of H 2 to the model planar phosphido complex [Ru(η 5 -indenyl)(PMe 2 )(PMe 3 )]. The latter study shows the intermediacy of an η 2 -H 2 adduct, [Ru(η 5 -indenyl)(PAr 2 )(η 2 -H 2 )(PPh 3 )], in the formation of [RuH(η 5 -indenyl)(HPMe 2 )(PMe 3 )], a further indication of the importance of the variable binding modes of the terminal phosphido ligand in this system.
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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 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.031 | 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".