Reactivity and Mechanism in the Oxidative Addition of Allylic Halides to a Dimethylplatinum(II) Complex
Bibliographic record
Abstract
The complex [PtMe 2 (2,2′-bipyridine)], 1, reacts with allyl chloride and allyl bromide, to give [PtXMe 2 (CH 2 CH═CH 2 )(2,2′-bipyridine)], 2, X = Cl; 3, X = Br, with 2-methylallyl chloride to give [PtClMe 2 (CH 2 CMe═CH 2 )(2,2′-bipyridine)], 4, and with crotyl chloride (a mixture of trans - and cis -MeCH═CHCH 2 Cl), to give a mixture of [PtClMe 2 ( trans- CH 2 CH═CHMe)(2,2′-bipyridine)], 5, and [PtClMe 2 ( cis- CH 2 CH═CHMe)(2,2′-bipyridine)], 6 . The complexes are formed mostly by trans oxidative addition and, for the crotyl complexes, without allylic rearrangement. Complex 1 reacts with CH 2 ═CHCHMeCl, mostly with allylic rearrangement, to give complex 5, with complexes 6 and [PtClMe 2 (CHMeCH═CH 2 )(2,2′-bipyridine)], 7, as minor products. The reactions of 1 with CH 2 ═CHCH 2 X (X = Cl or Br) and MeCH═CHCH 2 Cl follow second-order kinetics (first-order in both reagents), but 1 reacts with CH 2 ═CHCHMeCl by third-order kinetics (first-order in 1, second-order in CH 2 ═CHCHMeCl) and with CH 2 ═CMeCH 2 Cl by a mixture of second- and third-order kinetics. The second-order reactions are proposed to occur by the S N 2 mechanism, and potential mechanisms of the third-order reactions are discussed.
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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 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
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".