Oxidative Addition of Aryl Halides to Palladium(0) Complexes: A Density-Functional Study Including Solvation
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Bibliographic record
Abstract
Using density-functional theory calculations in combination with an electrostatic continuum solvation model, we have investigated the oxidative addition of phenyl halides PhX to palladium(0) complexes of bidentate phosphanes [Pd(PP)], yielding aryl halo complexes [(PP)Pd(Ph)(X)], with X = Cl, Br, I and PP = 1,2-bis(dimethylphosphino)ethane or ( P )-2,2‘-bis(dimethylphosphino)-1,1‘-biphenyl. We have considered the formation of the reactive 14-electron species from the saturated [Pd(PP) 2 ] as well as different prereaction complexes [(PP)Pd(PhX)] with an intact phenyl halide. We find that ligand dissociation is the limiting reaction step, while the formation of the prereaction complex and the oxidative addition itself are energetically (very) favorable. The concerted transition state for oxidative addition known in the gas phase could not be found in solution. Instead, we propose a pathway involving the very facile dissociation of the halide from the prereaction complex, with subsequent collapse to the product.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.019 | 0.000 |
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