Binuclear Dimethylplatinum(II) Complexes: Reactivity and Mechanism in Protonolysis and Oxidative Addition Reactions
Bibliographic record
Abstract
The reaction of [Pt 2 Me 4 (μ-SMe 2 ) 2 ] with the ligands 1,3- and 1,4-C 6 H 4 (CH NCH 2 CH 2 NMe 2 ) 2, 1,3-BAIB, and 1,4-BAIB, respectively, gave the corresponding complexes [Pt 2 Me 4 (1,3-BAIB)], 1, and [Pt 2 Me 4 (1,4-BAIB)], 2 . Complex 1 reacted with 2 equiv of HCl to give [(PtClMe) 2 (1,3-BAIB)], 3, in which the chloride ligands are trans to the imine nitrogen atoms. Complex 1 undergoes oxidative addition with methyl triflate to give, after recrystallization from moist solvent, the diplatinum(IV) aqua complex [{PtMe 3 (OH 2 )} 2 (1,3-BAIB)](CF 3 SO 3 ) 2, 4, which has the anti stereochemistry of the two aqua ligands. Complex 4 forms a dimer of dimers structure in the solid state through hydrogen bonding between aqua ligands and triflate anions. The reactions of 1 and 2 with HCl are shown to proceed through oxidative addition/reductive elimination sequences, and intermediate hydridoplatinum(IV) intermediates have been identified at low temperature by their 1 H NMR spectra. For example, in reactions with complex 1, binuclear hydride complexes of the types [(PtMe 2 )(PtHClMe 2 )(1,3-BAIB)], [(PtHClMe 2 ) 2 (1,3-BAIB)], and [(PtClMe)(PtHClMe 2 )(1,3-BAIB)] were identified. The initial oxidative addition reactions occur with trans stereochemistry, to give hydride trans to chloride, but isomerization was observed in some cases to give complexes with hydride trans to a nitrogen donor of the 1,3-BAIB ligand. The reactions with DCl or CF 3 SO 3 D in CD 3 OD or CD 3 OD/CD 3 CN solvent systems gave all isotopomers of methane CH n D 4 - n, indicating that there is an easy equilibrium between hydrido(methyl)platinum(IV) and (methane)platinum(II) complexes and easy hydrogen−deuterium exchange between hydridoplatinum groups and −OD groups of the solvent.
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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 | 0.001 | 0.001 |
| Research integrity | 0.001 | 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 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".