The one-electron oxidation of hydroxy(tetramesitylporphyrinato)iron(III)
Bibliographic record
Abstract
The oxidation of hydroxy(tetramesitylporphyrinato)Fe(III) ([Fe(tmp)]OH) has been investigated by voltammetric and spectroelectrochemical techniques in CH2Cl2 containing tetra(n-butyl)ammonium hexafluorophosphate as supporting electrolyte. In this medium, the first one-electron oxidation is reversible on the time scale of cyclic voltammetry. The UVvis spectrum, as obtained by double potential step chronoabsorptometry, indicates that the oxidation is centered at the porphyrin ring to form the corresponding π-cation radical. At longer times, or higher potentials, oxidation of [Fe(tmp)]OH leads to loss of hydroxide and formation of [Fe(tmp+)]PF6 π-cation radical. The time-dependent process is consistent with an ECE type mechanism, with the chemical step being slow conversion to neutral [Fe(tmp)]PF6. At higher potentials, the initial oxidation product loses a second electron. The overpotential dependent oxidation suggests an EEC type mechanism with the second electrochemical step being a slow heterogeneous electron transfer from the Fe-OH moiety.Key words: hydroxy(tetramesitylporphyrinato)iron(III), oxidation, electrochemistry, spectroelectrochemistry, π-cation radical.
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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".