Hydrogen peroxide as oxidant in bio-mimetic catalysis by manganese porphyrin: Theoretical DFT studies
Bibliographic record
Abstract
The aim of this study is to elucidate the geometry and electronic structure of various adducts that may be formed between manganese(III) (Mn(III)) porphyrin and hydrogen peroxide. Hydrogen peroxide may interact with Mn(III) porphyrin either as H2O2 or, after dissociation, as OOH–. In the former, it may decompose into two hydroxo groups, which acquire OH– character or an oxo group (=O) and a water molecule. Therefore, the following systems are considered: MnP(H2O2)+, MnP(H2O2)(OH), MnP(OH)3, [Formula: see text], MnPO+, MnPO(OH), MnP(OOH), MnP(OOH)(OH)–, and the possible transformations between them are taken into account. The reported studies are performed within the Density Functional Theory (DFT) method with the GGA-BP functional. The geometry and electronic structures of the structures found along the studied reaction pathways are discussed in terms of interatomic distances, valence angles, Mulliken charges, and spin densities. It was found that different active oxygen species may be formed in the reaction between Mn(III) porphyrin and hydrogen peroxide. As manganese is a transition metal, numerous possible spin states for each of the studied structures are found, where the relative energies of different multiplicities depend strongly on the ligands present in the complex. In view of the catalytic properties, all oxygen-containing ligands are negatively charged, which results in their behaviour as nucleophiles towards hydrocarbons. Finally, the analysis of charge and spin populations on different parts of the studied systems indicate the porphyrin ligand as active in charge transfer processes.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 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".