Synthesis of Highly Electron‐Deficient Iron(II)‐Porphyrins and Their Catalytic Efficiency for C─N Bond Formation Reactions
Bibliographic record
Abstract
Abstract Herein, we report the synthesis and characterization of highly electron‐deficient, air‐stable iron(II)porphyrin complex (1) [Fe II (TFPPCl 8 )(OHMe) 2 , H 2 TFPPCl 8 = tetrakis(pentafluorophenyl)‐2,3,7,8,12,13,17,18‐octachloroporphyrin, OHMe = methanol] and its catalytic activity toward olefin aziridination. The addition of highly electron‐withdrawing substituents at meso and β ‐positions on the periphery of the porphyrin macrocycle significantly distorts its geometric structure, and this modulation impacts its macrocycle properties while enabling the facile isolation of air‐stable high‐spin Fe(TFPPCl 8 )(OHMe) 2 in a highly nonplanar macrocyclic environment. The complex is structurally analyzed through single‐crystal X‐ray diffraction, and the supramolecular self‐assembly was investigated using density functional theory (DFT) and Hirshfeld analysis. Hirshfeld's study reveals the formation of halogen‐bonded supramolecular synthons involving fluorine and chlorine atoms on the porphyrin periphery. Catalytic aziridination on olefins was performed under mild conditions, showing that the catalyst is highly active toward aziridine formation under homogeneous conditions. The presence of strong electron‐withdrawing substituents (F and Cl) at the porphyrin periphery makes the metal center highly electron‐deficient and have high electron affinity, leading to variation in activity for substituted olefins. DFT calculations were performed to investigate the electronic structure of the (Por)Fe IV NTs species, which is an active site during catalysis reaction.
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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 | 0.000 |
| 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) | 0.000 | 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".