Substituent effects on gas‐phase homolytic Fe–N bond energies of <i>m</i>‐G‐C<sub>6</sub>H<sub>4</sub>NHFe(CO)<sub>2</sub>(η<sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>) and <i>m</i>‐G‐C<sub>6</sub>H<sub>4</sub>N(COMe)Fe(CO)<sub>2</sub>(η<sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>) studied using density functional theory methods
Bibliographic record
Abstract
Abstract One of the most fundamental properties in chemistry is the bond dissociation energy, the energy required to break a specific bond of a molecule. In this paper, the Fe–N homolytic bond dissociation energies [Δ H homo (Fe–N)'s] of 2 series of (meta‐substituted anilinyl)dicarbonyl(η 5 ‐cyclopentadienyl) iron [ m ‐G‐C 6 H 4 NHFp ( 1 )] and (meta‐substituted α‐acetylanilinyl)dicarbonyl(η 5 ‐cyclopentadienyl) iron [ m ‐G‐C 6 H 4 N(COMe)Fp ( 2 )] were studied using density functional theory methods with large basis sets. In this study, Fp is (η 5 ‐C 5 H 5 )Fe(CO) 2 , and G is NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 . The results show that Tao‐Perdew‐Staroverov‐Scuseria, Minnesota 2006, and Becke's power‐series ansatz from 1997 with dispersion corrections functionals can provide the best price/performance ratio and accurate predictions of Δ H homo (Fe–N)'s. The ΔΔ H homo (Fe–N)'s ( 1 and 2 ) conform to the captodative principle. The polar effects of the meta‐substituents show the dominant role to the magnitudes of ΔΔ H homo (Fe–N)'s. σ α · and σ c · values for meta‐substituents are all related to polar effects. Spin‐delocalization effects of the meta‐substituents in ΔΔ H homo (Fe–N)'s are small but not necessarily zero. RE plays an important role in determining the net substituent effects on Δ H homo (Fe–N)'s. Insight from this work may help the design of more effective catalytic processes.
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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 | 0.007 | 0.004 |
| Meta-epidemiology (narrow) | 0.013 | 0.014 |
| Meta-epidemiology (broad) | 0.016 | 0.009 |
| Bibliometrics | 0.003 | 0.006 |
| Science and technology studies | 0.008 | 0.008 |
| Scholarly communication | 0.003 | 0.007 |
| Open science | 0.008 | 0.007 |
| Research integrity | 0.004 | 0.015 |
| Insufficient payload (model declined to judge) | 0.000 | 0.001 |
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; both teacher heads agree on what is shown here.
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".