The Platinum Center is a Stronger Nucleophile than the Free Nitrogen Donors in a Dimethylplatinum Complex with a Dipyridylpyridazine Ligand
Bibliographic record
Abstract
The ligand 1,4-di-2-pyridyl-5,6,7,8,9,10-hexahydrocycloocta[ d ]pyridazine (6-dppd) contains two potential chelate groups, but it coordinates to only one dimethylplatinum group in forming the complex [PtMe 2 (6-dppd)], 1 . Complex 1 contains a free pyridyl and a free pyridazine nitrogen donor, but it fails to coordinate to ZnCl 2 or to CuCl to give a bimetallic complex. Complex 1 reacted with mercury(II) salts HgX 2 (X = Cl, Br, OAc), not by coordination but by oxidative addition to the dimethylplatinum(II) center to give the platinum(IV) complexes [PtX(HgX)Me 2 (6-dppd)]. Complex 1 reacted with bromine or iodine by trans oxidative addition to give [PtX 2 Me 2 (6-dppd)], X = Br or I, but, when X = I, a more complex sequence of reactions also gave rise to products of cis oxidative addition and to the products [PtIMe 3 (6-dppd)] and [PtI 3 Me(6-dppd)], which arise through a methyl group transfer reaction. Complex 1 reacted with alkyl halides RX by trans oxidative addition to give [PtXRMe 2 (6-dppd)], R = Me, X = I; R = CH 2 Ph, X = Br; R = CH 2 -4-C 6 H 4 -CH 2 Br, X = Br. The cleavage of methyl groups from complex 1 by DCl gave a mixture of all isotopomers of methane, CH 4– n D n, indicating ready equilibration between hydrido(methyl)platinum(IV) and methaneplatinum(II) complex intermediates.
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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 | 0.000 |
| 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".