New Bimetallic Reactivity in Pt<sub>2</sub><sup>II,II</sup>/Pt<sub>2</sub><sup>IV,IV</sup> Transformation Mediated by a Benzene Ring
Bibliographic record
Abstract
A new Pt 2 II,II complex with the formula Pt 2 (TPAB)Me 4 ( 1 ), where TPAB = 1,2,4,5-tetrakis(5-( p -C 7 H 15 Ph)-7-azaindol-1-yl)benzene, has been synthesized. This molecule has excellent solubility in common solvents, which enabled our investigation of its reactions with a variety of oxidants to form Pt 2 IV,IV species and the reverse reactions of the Pt 2 IV,IV species back to 1 via reduction. Despite the lack of direct Pt···Pt interactions, the two Pt centers in 1 display distinct bimetallic cooperativity mediated by the central phenyl ring of the TPAB ligand. The most unusual finding is that the reactivity of 1 with MeOTf is highly dependent on the amount of molecular oxygen present in the reaction medium. In the absence of O 2, the reaction of 1 with MeOTf produced [Pt 2 IV,IV (TPAB)Me 6 ][OTf] 2 ( 6 ), while in the presence of O 2, complex 7, Pt 2 IV,IV (TPAB)Me 4 (OTf) 2, was obtained. Compound 1 was found to react readily with O 2 at one atmosphere and ambient temperature to produce an insoluble and not yet fully characterized solid that further reacts with MeOTf to produce 7 quantitatively. NMR and single-crystal X-ray diffraction analyses established that the two Pt IV centers in 6 are five-coordinate with a square-pyramidal geometry, while in 7 the two Pt IV centers are six-coordinate with an octahedral geometry. Most significantly, the central phenyl ring of the TPAB ligand was transformed to a cyclohexyldienyl in 7, while it remains unchanged in 6 . Complex 1 also reacts readily with other oxidants such as CHCl 3, PhICl 2, Br 2 (CBr 4 ), I 2, and H 2 O 2 to produce Pt 2 IV,IV (TPAB)Me 4 X 2 (X = Cl, 2; Br, 3; I, 4; OH, 5 ). The structures of 2 − 5 are similar to that of 7, showing the generality of the central phenyl ring mediated oxidation of the Pt 2 II,II system. Complexes 2 and 7 can be reduced and converted back to complex 1 via reactions with BH 4 −, as established by NMR experiments.
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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) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.001 | 0.004 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.000 | 0.002 |
| Open science | 0.002 | 0.000 |
| Research integrity | 0.001 | 0.002 |
| Insufficient payload (model declined to judge) | 0.005 | 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; both teacher heads agree on what is shown here.
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".