Remote substituent effects on homolytic 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>(COMe)NFe(CO)<sub>2</sub>(η<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
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
Bibliographic record
Abstract
The nature and strength of metal–ligand bonds in organotransition–metal complexes is crucial to the understanding of organometallic reactions and catalysis. The Fe‐N homolytic bond dissociation energies [Δ H homo (Fe‐N)′s] of two series of para‐substituted Fp anilines p ‐G‐C 6 H 4 NHFp [1] and p ‐G‐C 6 H 4 N(COMe)Fp [2] were studied using the Hartree–Fock (HF) and the density functional theory 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 BP86 and TPSSTPSS can provide the best price/performance ratio and accurate predictions of Δ H homo (Fe‐N)′s. B3LYP can also satisfactorily predict the α and remote substituent effects on Δ H homo (Fe‐N)′s [ΔΔ H homo (Fe‐N)′s]. The good correlations [ r = 0.96 (g, 1), 0.99(g, 2)] of ΔΔ H homo (Fe‐N)′s in series 1 and 2 with the substituent σ p + constants imply that the para‐substituent effects on Δ H homo (Fe‐N)′s originate mainly from polar effects, but those on radical stability originate from both spin delocalization and polar effects. ΔΔ H homo (Fe‐N)′s(1,2) conform to the captodative principle. Insight from this work may help the design of more effective catalytic processes. Copyright © 2012 John Wiley & Sons, Ltd.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.011 | 0.007 |
| Meta-epidemiology (narrow) | 0.013 | 0.013 |
| Meta-epidemiology (broad) | 0.015 | 0.008 |
| Bibliometrics | 0.003 | 0.007 |
| Science and technology studies | 0.006 | 0.008 |
| Scholarly communication | 0.003 | 0.006 |
| Open science | 0.006 | 0.005 |
| Research integrity | 0.008 | 0.016 |
| 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