The sequential insertion of carbon monoxide and imines into nickel-carbon sigma-bonds and kinetic analysis of imine insertion into palladium-acyl sigma-bonds
Bibliographic record
Abstract
ABSTRACT The Sequential Insertion of Carbon Monoxide and Imines into Nickel-Carbon Sigma-Bonds and Kinetic Analysis of Imine Insertion into Palladium-Acyl Sigma-Bonds The coupling of imines and carbon monoxide mediated by late transition metals has been previously reported in the Arndtsen laboratory. The fundamental properties of 2,1-migratory insertion of imines into nickel- and palladium-acyl bonds are presented in this text. This study investigates the use of neutral eta2-N,O-salicylaldiminato nickel (II) systems (Chapter 2) as potential complexes to mediate the sequential insertion of carbon monoxide and imines. These complexes undergo rapid carbon monoxide insertion. Subsequent imine insertion is permitted when the imine substrate is sterically unencumbered. The coupling product disproportionates leading to the formation of 1,2-diamides. In our laboratory, kinetic and thermodynamic studies on the coordination and 2,1-migratory insertion of imines into palladium-carbon sigma-bonds were the focus of former student Rania Dghaym, Ph.D. Chapter 3 completes these studies, and offers a mechanistic picture of the pathway by which 2,1-migratory insertion into palladium-acyl bonds proceeds. Our mechanistic data suggest that imine insertion is distinct from olefin insertion and involves the concerted migratory attack of the sigma-coordinated imine to the electrophilic acyl ligand.
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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".