Ruthenated Acetonitrile: Unusual Brønsted Acidity of a Polar “Aprotic” Solvent
Bibliographic record
Abstract
Addition of acetonitrile to the complex [Ru(η 5 -indenyl)(PR 2 )(PPh 3 )] ( 1 ) gives the unusual metalation product [Ru(η 5 -indenyl)(CH 2 CN)(HPR 2 )(PPh 3 )] ( 2 ), which has been structurally characterized. This reaction clearly demonstrates high Brønsted basicity at the terminal phosphido ligand in 1 . 31 P{ 1 H} NMR studies show that less acidic N-donor solvents simply disrupt the Ru−P π-bond in 1 to give adducts [Ru(η 5 -indenyl)(L)(HPR 2 )(PPh 3 )] (L = benzonitrile ( 6 ) or pyridine ( 7 )), which are in equilibrium with 1 and free L. The analogous acetonitrile adduct ( 4 ) was observed by NMR at 240 K during the formation of 2, but is quickly replaced by 2 at higher temperatures. NMR studies of an alternate route to the metalated complex 2, starting from the cationic N-bound acetonitrile adduct [Ru(η 5 -indenyl)(NCCH 3 )(HPCy 2 )(PPh 3 )][PF 6 ] ( 3a ), along with the demonstrated lability of the benzonitrile and pyridine adducts, suggest that the metalation of acetonitrile by 1 proceeds via an intermolecular C−H addition across the Ru═P double bond, rather than the intramolecular C−H activation of N-bound acetonitrile. This is confirmed by the observation, by 31 P{ 1 H} NMR, of multiple product isotopomers in the reaction of 1 with a 1:1 mixture of d 3 - and d 0 -acetonitrile. O-Donor solvents also deprotonated by 1 include water, alcohols, and acetone, which give the complexes [Ru(η 5 -indenyl)(X)(HPCy 2 )(PPh 3 )], where X = OR ( 8 ), CH 2 (═O)CH 3 ( 10 ).
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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 | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.046 | 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".