Enhanced Catalytic Activity of Iridium(III) Complexes by Facile Modification of C,N-Bidentate Chelating Pyridylideneamide Ligands
Bibliographic record
Abstract
A set of aryl-substituted pyridylideneamide (PYA) ligands with variable donor properties owing to a pronounced zwitterionic and a neutral diene-type resonance structure were used as electronically flexible ligands at a pentamethylcyclopentadienyl (Cp*) iridium center. The straightforward synthesis of this type of ligand allows for an easy incorporation of donor substituents such as methoxy groups in different positions of the phenyl ring of the C,N-bidentate chelating PYA. These modifications considerably enhance the catalytic activity of the coordinated iridium center toward the catalytic aerobic transfer hydrogenation of carbonyls and imines as well as the hydrosilylation of phenylacetylene. Moreover, these PYA iridium complexes catalyze the base-free transfer hydrogenation of aldehydes, and to a lesser extent also of ketones. Under standard transfer hydrogenation conditions including base, aldehydes are rapidly oxidized to carboxylic acids rather than reduced to the corresponding alcohol, as is observed under base-free conditions.
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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".