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 machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| 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) | 0.002 | 0.001 |
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 source (direct Gemma or distilled Codex), 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".