Formation and Reactivity of a Biomimetic Hydroperoxocopper(II) Cryptate
Bibliographic record
Abstract
Abstract Copper(II)‐hydroperoxo species are proposed as key intermediates in the catalytic cycles of copper‐monooxygenase enzymes that perform C–H bond hydroxylation. Herein we report on the oxidation chemistry of a copper(II) complex with a coordinating cryptand based on a peralkylated tetradentate tris(2‐aminoethyl)amine (tren) moiety. X‐ray crystallography of the copper(II) acetate complex of this cryptand revealed that the copper(II) ion is in a square‐pyramidal environment, with the cryptand acting only as a tridentate ligand. This geometry is conserved in solution and likely results from restraints imposed by the semi‐rigid cryptand. Reaction of this complex with basic hydrogen peroxide in methanol led to the decomposition of the complex with an oxygen‐atom transfer to the ligand, as evidenced by mass spectrometry analysis after reaction and demetallation. Low‐temperature stopped‐flow experiments (down to –90 °C) support the formation of a copper(II)‐hydroperoxo intermediate, CuOOH, before ligand oxygenation occurs. It is proposed that this intermediate performs the oxygen‐atom transfer to a weak benzylic C–H bond of the cryptand, thereby mimicking the behavior of dopamine‐β‐hydroxylase.
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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".