Transmetalation reactions with nitrogen-containing "pincer"-class ligands on platinum(II) centers
Bibliographic record
Abstract
The transmetalation reaction of the aryllithium compound [Li(NCN)] 2 (NCN is the monoanionic "pincer" ligand [C 6 H 3 (CH 2 NMe 2 ) 2 -2,6] - ) with the cyclometalated arylplatinum complex [PtCl(NCN)] afforded the bisaryl platinum(II) complex [Pt(NCN) 2 ] (3) containing one η 3 -N,C,N-terdentate and the other η 1 -C-monodentate-bonded pincer ligand. Spectroscopic analyses on 3 suggest that η 3 to η 1 interconversion of the ligand binding mode (or vice versa) is inhibited. Two independent X-ray structure determinations on crystals of 3 revealed the existence of a rare polymorph containing one and three crystallographically independent molecules, respectively, in the unit cell. A similar transmetalation reaction with lithium and platinum complexes containing heteroleptic NCN RR' ligands (NCN RR' is [C 6 H 3 (CH 2 NRR')-2,6] - with R = R' = Me or R = Me, R' = Et) pointed to the formation of a heterodinuclear cationic bisaryl platinum lithium species as an intermediate of a preequilibrium to the final transmetalation products, involving, rapid transcyclometalation (TCM) reactions. These TCM reactions comprise the exchange of the monoanionic NCN RR' ligands between the platinum(II) and lithium centers. A consequence of the latter properties is that the strong PtN bonds in [PtX(NCN)] complexes are considerably weakened by the presence of Li + cations.Key words: transmetalation, transcyclometalation (TCM), platinum, bisaryl complex, polymorphism.
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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 | 0.000 | 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 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 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".