Lewis-Acidity of Trimethylplatinum(IV) with Labile Oxygen-Donor Ligands
Bibliographic record
Abstract
Trimethylplatinum(IV) systems with labile ligands and weakly coordinating anions were investigated with respect to their Lewis-acidity and their ability to act as Lewis-acidic catalysts. The Lewis-acidity of tetrameric trimethylplatinum(IV) triflate (triflate = trifluoromethanesulfonate, OTf), [{Me 3 PtOTf} 4 ], toward carbonyl compounds was quantified by NMR titration with crotonaldehyde (Childs' method) in CD 2 Cl 2 . The data show moderate but significant Lewis-acidity of the trimethyl platinum(IV) center (27% of the acidity of BBr 3 ) and commensurate (moderate) intrinsic catalytic activity of the trimethylplatinum(IV) unit. Crystals of an aldehyde adduct were obtained. X-ray crystallography shows a binuclear metal complex, [{Me 3 Pt(crotonaldehyde)(μ-OTf)} 2 ]. Despite the relatively low Lewis-acidity, in the absence of oxygen-donor ligands, the trimethylplatinum(IV) is capable of decomposing the [B(Ar F ) 4 ] - anion (Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) to yield B(Ar F ) 3, apparently via aryl abstraction. Salt metathesis reactions of [{Me 3 PtOTf} 4 ] with Na[B(Ar F ) 4 ] in the presence of oxygen-donor ligands lead to mixtures that are highly catalytically active in the diastereoselective Mukaiyama-aldol reaction, likely via generation of very electrophilic silicon species.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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) | 0.001 | 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".