Intramolecular Csp<sup>3</sup>-H Activation at a Platinum(IV) Center Resulting from O<sub>2</sub> Activation: The Role of a Proton-Responsive Ligand and Trans Influence
Bibliographic record
Abstract
Aerobic oxidation of a dimethylplatinum(II) complex featuring 1,1-di(2-pyridyl)ethanol as a supporting ligand leads to the formation of two unexpected Pt IV complexes (in ∼1:1 ratio), neither of which results from direct oxidation typical for Pt II centers supported by popular κ 2 -( N, N ) ligands. While one product features an isomerized Pt IV center stabilized by the κ 3 -( N, N, O ) ligand coordination mode, surprisingly, the other product results from intramolecular activation of the ligand methyl fragment. Mechanistic studies, reactivity of model complexes, and DFT calculations reveal that the critical proton-responsive nature of the ligand allows formation of intermediates that result in a concerted metalation deprotonation (CMD)-like C–H activation at Pt IV . To the best of our knowledge, this is the first mechanistic delineation of Csp 3 -H activation at Pt IV, despite being known for other high-valent platinum group metal centers.
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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 | 0.000 |
| 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 | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 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 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".