Hartree–Fock and density functional theory study of remote substituent effects on heterolytic Fe–N bond energies of <i>p</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>p</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>)
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Bibliographic record
Abstract
The nature and strength of metal–ligand bonds in organotransition‐metal complexes are crucial to the understanding of organometallic reactions and catalysis. Quantum chemical calculations at different levels of theory have been used to investigate heterolytic Fe–N bond energies of para‐substituted anilinyldicarbonyl(η 5 ‐cyclopentadienyl)iron [ p ‐G‐C 6 H 4 NH(η 5 ‐C 5 H 5 )Fe(CO) 2 , abbreviated as p ‐G‐C 6 H 4 NHFp (1), where G = NO 2 , CN, COMe, CO 2 Me, CF 3 , Br, Cl, F, H, Me, MeO, and NMe 2 ] and para‐substituted α‐acetylanilinyldicarbonyl(η 5 ‐cyclopentadienyl)iron [ p ‐G‐C 6 H 4 N(COMe)(η 5 ‐C 5 H 5 )Fe(CO) 2 , abbreviated as p ‐G‐C 6 H 4 N(COMe)Fp (2)] complexes. The results show that BP86 and TPSSTPSS can provide the best price/performance ratio and more accurate predictions in the study of Δ H het (Fe–N)'s. The linear correlations [ r = 0.98 (g, 1a), 0.93 (g, 2b)] between the substituent effects of heterolytic Fe–N bond energies [ΔΔ H het (Fe–N)'s] of series 1 and 2 and the differences of acidic dissociation constants (Δp K a ) of N–H bonds of p ‐G‐C 6 H 4 NH 2 and p ‐G‐C 6 H 4 NH(COMe) imply that the governing structural factors for these bond scissions are similar. And the linear correlations [ r = −0.99 (g, 1c), −0.92 (g, 2d)] between ΔΔ H het (Fe–N)'s and the substituent σ p − constants show that these correlations are in accordance with Hammett linear free energy relationships. The polar effects of these substituents and the basis set effects influence the accuracy of Δ H het (Fe–N)'s. ΔΔ H het (Fe–N)'s(1, 2) follow the captodative principle. ME α‐COMe, para‐G s include the influences of the whole molecules. The correlation of ME α‐COMe, para‐G s with σ p − is excellent. ME α‐COMe, para‐G s rather than ΔΔ H het (Fe–N)'s in series 2 are more suitable indexes for the overall substituent effects on Δ H het (Fe–N)'s(2). Insight from this work may help the design of more effective catalytic processes. Copyright © 2012 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 | 0.005 | 0.002 |
| Meta-epidemiology (narrow) | 0.011 | 0.012 |
| Meta-epidemiology (broad) | 0.014 | 0.007 |
| Bibliometrics | 0.002 | 0.006 |
| Science and technology studies | 0.004 | 0.006 |
| Scholarly communication | 0.002 | 0.006 |
| Open science | 0.005 | 0.005 |
| Research integrity | 0.004 | 0.013 |
| Insufficient payload (model declined to judge) | 0.000 | 0.001 |
Machine scores (provisional)
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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