Substituent effects on gas‐phase homolytic Fe–O and Fe–S bond energies of <i>m</i>‐G‐C<sub>6</sub>H<sub>4</sub>OFe(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>SFe(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
Bibliographic record
Abstract
The thermochemistry of organometallic complexes in solution and in the gas phase has been an area of increasing research interest. 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 meta‐substituted phenoxydicarbonyl(η 5 ‐cyclopentadienyl) iron [ m ‐G‐C 6 H 4 OFp ( 1 )] and (meta‐substituted benzenethiolato)dicarbonyl(η 5 ‐cyclopentadienyl) iron [ m ‐G‐C 6 H 4 SFp ( 2 )] were studied using Hartree–Fock and 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 Tao–Perdew–Staroverov–Scuseria and Minnesota 2006 functionals 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 polar effects of the meta substituents show that the dominant role to the magnitudes of ΔΔ H homo (Fe–O)'s or ΔΔ H homo (Fe–S)'s. σ α ·, σ c · values for meta substituents are all related to polar effects. Spin‐delocalization effects of the meta substituents in ΔΔ H homo (Fe–O)'s and ΔΔ H homo (Fe–S)'s are small but not necessarily zero. Molecular effects rather than ΔΔ H homo (Fe–O)'s and ΔΔ H homo (Fe–S)'s are more suitable indexes for the overall substituent effects on Δ H homo (Fe–O)'s and Δ H homo (Fe–S)'s. The meta substituent effects of meta‐electron‐withdrawing groups on the Fe–S bonds are much stronger than those on the Fe–O bonds. For meta‐electron‐donating groups, the meta substituent effects have the comparable magnitudes between series 1 and 2 . 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 © 2015 John Wiley & Sons, Ltd.
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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 | 0.010 | 0.007 |
| Meta-epidemiology (narrow) | 0.012 | 0.012 |
| Meta-epidemiology (broad) | 0.014 | 0.006 |
| Bibliometrics | 0.003 | 0.007 |
| Science and technology studies | 0.005 | 0.008 |
| Scholarly communication | 0.003 | 0.005 |
| Open science | 0.005 | 0.005 |
| Research integrity | 0.007 | 0.014 |
| 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".