Metal-Ion Influence on Ligand-Centered Hydrogen-Atom Transfer
Bibliographic record
Abstract
The ligand-centered hydrogen-atom-transfer (HAT) reactivity was examined for a family of group 10 metal complexes containing a tridentate pincer ligand derived from bis(2-mercapto-p-tolyl)amine, [SNS]H3. Six new metal complexes of palladium and platinum were synthesized with the [SNS] ligand platform in different redox and protonation states to complete the group 10 series previously reported with nickel. The HAT reactivity was examined for this family of nickel, palladium, and platinum complexes to determine the impact of a metal ion on the ligand-centered reactivity. Thermodynamic measurements revealed that N–H bond dissociation free energies increased by approximately 10 kcal mol–1 along the series Ni < Pd < Pt driven by changes to both the redox potential and pKa of the ligand. Kinetic analyses for all three metal complexes suggest that the barrier to the HAT reactivity is primarily entropic rather than enthalpic for this system.
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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 | 0.000 | 0.000 |
| 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 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.010 | 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 teacher head, 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".