Study of aerobic oxidation of phenyl Pt<sup>II</sup> complexes (dpms)Pt<sup>II</sup>Ph(L) (dpms = di(2-pyridyl)methanesulfonate; L = water, methanol, or aniline)
Bibliographic record
Abstract
Oxidation of phenyl Pt II complexes K[(dpms)Pt II Ph 2 ], 1, (dpms)Pt II Ph(MeOH), 2, (dpms)Pt II Ph(OH 2 ), 3, and methyl Pt II complex (dpms)Pt II Me(NH 2 Ph), 6, with O 2 in aqueous or methanol solutions under ambient conditions leads to corresponding (dpms)Pt IV R(X)OH complexes (R = X = Ph, 7; R = Ph, X = OH, 8; R = Ph, X = OMe, 9; R = Me, X = NHPh; 11; dpms = di(2-pyridyl)methanesulfonate). Complexes 7–9 could be isolated in high yield. Complex 11 as well as its phenyl analogue (dpms)Pt IV Ph(NHPh)OH, 10 can be prepared in high yield by oxidation of corresponding (dpms)Pt II R(NH 2 Ph) with H 2 O 2 in methanol. Phenyl Pt II complexes (dpms)Pt II Ph(HX) derived from HX = aniline and DMSO, 4 and 5, respectively, are inert toward O 2 . The rate of oxidation of 1–5 with O 2 decreases in the order 1 > 3 ~ 2 » 4, and 5 is unreactive. Methyl analogues are significantly more reactive compared with their phenyl counterparts. Proposed mechanism of oxidation with O 2 includes formation of anionic species (dpms)Pt II R(X) – responsible for reaction with dioxygen. Attempts at C–O and C–N reductive elimination from phenyl Pt IV complexes 7–10 do not lead to phenyl derivatives PhX at 80–100 °C, consistent with the results of the DFT estimates of corresponding activation barriers, ΔG 0 exceeding 28 kcal/mol.Key words: platinum phenyl complexes, oxidation, dioxygen, aqueous solution, mechanism.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.002 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.006 | 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 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".