Potential Energy Surfaces in Transition States for Associative Reactions of Metal Carbonyl Clusters: Reactions of Rh<sub>4</sub>(CO)<sub>12</sub> with P-Donor Nucleophiles
Bibliographic record
Abstract
The metal carbonyl cluster Rh 4 (CO) 12 reacts with a wide variety of P-donor nucleophiles solely by an associative mechanism, and the rate constants can be analyzed quantitatively according to the electronic and steric properties of the nucleophiles by the QALE method. An unexpected outcome of this analysis is that inclusion of what has become known as the “aryl effect” is clearly necessary, together with positive contributions to the rates of effects due to the π-acidity of the phosphite nucleophiles. A simple way of representing the individual contributions of the various effects to the overall rates is described, and the general σ-basicity and steric effects can be represented graphically by a three-dimensional “log k 2 surface” upon which the aryl and π-acidity effects can separately be superimposed as additional peaks. A free energy surface can be obtained by a simple scale change.
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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 | 0.001 | 0.002 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.002 | 0.001 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.002 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.002 | 0.001 |
| Insufficient payload (model declined to judge) | 0.007 | 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".