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 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 | 0.000 |
| 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 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".