Remote substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of <i>p</i>‐G‐C<sub>6</sub>H<sub>4</sub>OFe(CO)<sub>2</sub>(<i>η</i><sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>) and <i>p</i>‐G‐C<sub>6</sub>H<sub>4</sub>SFe(CO)<sub>2</sub>(<i>η</i><sup>5</sup>‐C<sub>5</sub>H<sub>5</sub>) studied using Hartree–Fock and density functional theory methods
Why this work is in the frame
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Bibliographic record
Abstract
Metal–ligand bond enthalpy data can afford invaluable insights into important reaction patterns in organometallic chemistry and catalysis. In this paper, the Fe–O and Fe–S homolytic bond dissociation energies [Δ H homo (Fe–O)'s and Δ H homo (Fe–S)'s] of two series of para‐substituted phenoxydicarbonyl( η 5 ‐cyclopentadienyl) iron [ p ‐G‐C 6 H 4 OFp ( 1 )] and (para‐substituted benzenethiolato)dicarbonyl( η 5 ‐cyclopentadienyl) iron [ p ‐G‐C 6 H 4 SFp ( 2 )] were studied using Hartree–Fock and density functional theory (DFT) methods with large basis sets. In this study, Fp is ( η 5 ‐C 5 H 5 )Fe(CO) 2 , and G are NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 . The results show that DFT methods can provide the best price/performance ratio and accurate predictions of Δ H homo (Fe–O)'s and Δ H homo (Fe–S)'s. The remote substituent effects on Δ H homo (Fe–O)'s and Δ H homo (Fe–S)'s [ΔΔ H homo (Fe–O)'s and ΔΔ H homo (Fe–S)'s] can also be satisfactorily predicted. The good correlations [ r = 0.98 (g, 1), 0.98 (g, 2)] of ΔΔ H homo (Fe–O)'s and ΔΔ H homo (Fe–S)'s in series 1 and 2 with the substituent σ p + constants imply that the para‐substituent effects on Δ H homo (Fe–O)'s and Δ H homo (Fe–S)'s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔ H homo (Fe–O)'s ( 1 ) and ΔΔ H homo (Fe–S)'s ( 2 ) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes. Copyright © 2013 John Wiley & Sons, Ltd.
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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 | 0.009 | 0.006 |
| Meta-epidemiology (narrow) | 0.012 | 0.013 |
| Meta-epidemiology (broad) | 0.014 | 0.007 |
| Bibliometrics | 0.003 | 0.007 |
| Science and technology studies | 0.005 | 0.008 |
| Scholarly communication | 0.003 | 0.006 |
| Open science | 0.005 | 0.005 |
| Research integrity | 0.007 | 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 it