A Kinetics Study of the Oxidative Addition of Bromobenzene to Pd(PCy<sub>3</sub>)<sub>2</sub>(Cy = cyclohexyl) in a Nonpolar Medium: The Influence on Rates of Added PCy<sub>3</sub>and Bromide Ion
Bibliographic record
Abstract
Bromobenzene oxidatively adds to the palladium(0) compound Pd(PCy 3 ) 2 to give cleanly the palladium(II) product trans -PdBr(Ph)(PCy 3 ) 2 . Kinetics studies of this reaction under pseudo-first-order conditions (excess PhBr) as well as in the presence of 1 molar equiv of PCy 3 or of added bromide ion (as the toluene-soluble tetraoctylphosphonium salt) have been carried out. We find that oxidative addition is first-order in palladium and that, in the absence of added PCy 3, the reaction involves both the 2:1 species Pd(PCy 3 ) 2 and the 1:1 species Pd(PCy 3 ). Interestingly, added PCy 3 results in inhibition of oxidative addition both by decreasing the relative amount of the reactive 1:1 compound and by converting much of the palladium(0) to the kinetically less active 3:1 compound Pd(PCy 3 ) 3 . Added bromide ion has essentially no effect on the rate, surprising in view of previous literature reports.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 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; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
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".