Use of the Imine–Enamine Equilibrium in Cooperative Ligand Design
Bibliographic record
Abstract
The imine–phosphine ligands Ph 2 PC 5 H 7 NAr, where Ar = 2,6-Pr i 2 C 6 H 3, 2,6-Me 2 C 6 H 3, were deprotonated using KH to generate the corresponding potassium salts, which were reacted with [(COD)IrCl] 2 to generate the enamidophosphine derivatives (COD)Ir(Ph 2 PC 5 H 6 NAr) (Ar = 2,6-Pr i 2 C 6 H 3, 4a; Ar = 2,6-Me 2 C 6 H 3, 4b ). These complexes were exposed to alcohols, H 2, and CO to generate a series of products, some of which involve protonation of the enamido unit to generate the imine tautomer. The reaction of 4a with isopropyl alcohol or H 2 generates the dinuclear hexahydride [(Ph 2 PC 5 H 7 N-2,6-Pr i 2 C 6 H 3 )IrH 2 ] 2 (μ-H) 2 ( 5a ), while the reaction with primary alcohols generates the dicarbonyl enamidophosphine complex (CO) 2 Ir(Ph 2 PC 5 H 6 NAr) ( 6a ). The reaction of the hexahydride 5a with CO generates 6a, for which a mechanism is proposed on the basis of monitoring this reaction as a function of time by NMR spectroscopy. On the basis of these experiments, cooperative ligand effects can be replicated by imine–phosphine ligands by proton transfer to and from the ligand backbone.
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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) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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 | 0.000 |
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".