Transmetalation of a Primary Amino-Functionalized N-Heterocyclic Carbene Ligand from an Axially Chiral Square-Planar Nickel(II) Complex to a Ruthenium(II) Precatalyst for the Transfer Hydrogenation of Ketones
Bibliographic record
Abstract
The first homoleptic nickel(II) complex with primary amino-functionalized N-heterocyclic carbene (C−NH 2 ) ligands ([Ni( m -CH 2 NH 2 ) 2 ](PF 6 ) 2, 2 ) was prepared under mild conditions by the reduction of a nitrile-functionalized imidazolium salt. This axially chiral, square-planar nickel(II) complex was characterized by NMR spectroscopy and an X-ray diffraction study. Enantiopure Δ-TRISPHAT was used as an NMR chiral shift reagent to observe the diastereotopic ion pairs by 1 H NMR in acetonitrile- d 3 . A novel transmetalation reaction moved the primary amino-functionalized N-heterocyclic carbene ligand from the nickel(II) complex 2 to the [Ru( p -cymene)Cl] 2 dimer, yielding the complex [Ru( p -cymene)( m -CH 2 NH 2 )Cl]PF 6, ( 3 ), the first ruthenium(II) complex with such a chelating C−NH 2 ligand. Complex 3 is a precatalyst for the transfer hydrogenation of acetophenone to 1-phenylethanol in basic 2-propanol at 75 °C with a turnover frequency of up to 880 h −1 and conversion of 96%.
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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) | 0.001 | 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 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".