Protonolysis of Dimethylplatinum(II) Complexes: Primary Attack at Metal or Ligand
Bibliographic record
Abstract
The complexes [PtMe 2 (DMEP)], 1, and [PtMe 2 (DMPP)], 2 [DMEP, DMPP = Me 2 N(CH 2 ) n N CH-2-C 5 H 4 N, n = 2, 3, respectively], contain ligands that chelate to platinum through the imine and pyridyl groups, with the tertiary amine group not coordinated. Methyl iodide reacted with complex 1 to give [PtIMe 3 (DMEP)] but reacted with 2 to give a mixture of [PtIMe 3 (DMPP)] and [PtMe 3 (DMPP)]I, indicating the greater ability of DMPP to act as a fac -tridentate ligand. Complex 2 reacted with MeO 3 SCF 3 to form [PtMe 3 (DMPP)][CF 3 SO 3 ] only. The primary reaction of 1 and 2 with HX (X = Cl, O 2 CCF 3, or O 3 SCF 3 ) occurred by protonation of the pendant amine, while with excess acid, a methylplatinum bond trans to imine was cleaved selectively. Two products of protonolysis, namely [PtMe(DMEP)][O 3 SCF 3 ], containing mer -tridentate DMEP, and [PtMe(O 2 CCF 3 )(DMEPH)][O 2 CCF 3 ], with a protonated bidentate DMEP ligand, have been characterized by structure determinations, and the reaction pathways have been deduced by monitoring the reactions by 1 H NMR at varying temperature. In the reaction of 2 with HCl, an intermediate hydridoplatinum(IV) complex [PtHClMe 2 (DMPPH)][Cl] was detected and determined to be stable up to −30 °C, when it decomposed to give methane and [PtClMe(DMPPH)][Cl].
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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".