Density Functional Theory Study of Redox Pairs. 1. Dinuclear Iron Complexes That Undergo Multielectron Redox Reactions Accompanied by a Reversible Structural Change
Bibliographic record
Abstract
The single two-electron reduction for the Fe−Fe bonded dinuclear complexes Fe 2 (CO) 6 (μ 2 -PR 2 ) 2 (R = CH 3, 1-CH 3; R = CF 3, 1-CF 3 ) is studied by electronic structure calculations based on density functional theory (DFT) methods. Several theoretical models are evaluated, including gas-phase models and models that include solvation (COSMO model) and/or countercations. The experimentally observed cleavage of the Fe−Fe bond upon addition of electrons is reproduced in all calculations. The different theoretical models are evaluated by calculating the energy of the disproportionation reaction 2A - → A + A 2 - using the energies of the complexes [1-R] 0, [1-R] -, and [1-R] 2 - . As expected, gas-phase calculations poorly model the experimental redox behavior, and the inclusion of solvation or countercations is necessary to correctly predict that the disproportionation reaction is energetically downhill. The distribution of the added electrons over the molecules and the charge distribution as a function of alkali metal countercation (Li +, Na +, K + ) are evaluated using the Hirshfeld charge analysis scheme. A qualitative correlation is found between the HOMO/LUMO energies of the redox species and the calculated redox potentials.
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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 | 0.001 | 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 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.002 | 0.001 |
| Insufficient payload (model declined to judge) | 0.006 | 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".