Hydrogenation of Benzonitrile to Benzylamine Catalyzed by Ruthenium Hydride Complexes with P−NH−NH−P Tetradentate Ligands: Evidence for a Hydridic−Protonic Outer Sphere Mechanism
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Bibliographic record
Abstract
The reaction of RuHCl(PPh 3 ) 3 with the tetradentate ligand [PPh 2 (( ortho -C 6 H 4 )CH 2 NHCH 2 - )] 2 {ethP 2 (NH) 2 } in THF produces the new complex trans -RuHCl{ethP 2 (NH) 2 } ( 1 ) as a mixture of two isomers. The complex RuHCl{ethP 2 (NH) 2 } ( 1 ) when activated with KO t Bu/KH is a very active catalyst for the hydrogenation of benzonitrile to benzylamine in toluene, more active than the known catalyst Ru(H 2 ) 2 H 2 (PCy 3 ) 2 ( 2 ). A mixture of 1 and 2 and base also results in efficient conversion of benzonitrile to benzylamine. The complex RuHCl{tmeP 2 (NH) 2 } ( 3 ) where tmeP 2 (NH) 2 is [PPh 2 (( ortho -C 6 H 4 )CH 2 NHCMe 2 - )] 2 is a less active catalyst for this reaction. These catalyst systems are air sensitive and extremely moisture sensitive. Experimental and theoretical (DFT) evidence is presented for a new mechanism for nitrile hydrogenation: the successive hydrogenation of the CN triple bond and then the CN double bond of the intermediate imine by H + /H - transfer from a trans dihydride active catalyst. The amido complex RuH{tmeP 2 N(NH)} ( 4 ) has similar activity to 3 /base for the base-free hydrogenation of benzonitrile and is moderately active for the catalytic hydration of benzonitrile. The new complex RuH(BH 4 ){ethP 2 (NH) 2 } ( 7 ) was prepared by reacting 1 with NaBH 4 but is found to be a poor catalyst for nitrile hydration.
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.002 |
| 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) | 0.001 | 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 it