P,N-Chelate Complexes of Pd(II) and Pt(II) Based on a Phosphaalkene Motif: A Catalyst for the Overman−Claisen Rearrangement
Bibliographic record
Abstract
The reaction of E / Z -MesP C(Ph)(Py) ( 1, Mes = 2,4,6-Me 3 C 6 H 2 - ) with (cod)PtCl 2 or (cod)PdCl 2 affords P,N-chelate complexes [MesP C(Ph)(Py)PtCl 2 ] ( 2a ) and [MesP C(Ph)(Py)PdCl 2 ] (2b ), respectively. Compounds 2a and 2b were fully characterized spectroscopically, and both were characterized by X-ray crystallography. The molecular structures exhibited almost identical metrical parameters. The P C bond lengths in 2a and 2b [1.672(4) and 1.675(3) Å, respectively] were shortened substantially with respect to that of 1 [1.7043(16) Å]. Complex 2b was explored as a catalyst for the Overman−Claisen rearrangement. Several allyl trichloroacetimidate substrates [HN C(CCl 3 )OCH 2 CH CHR 1: 3a, R 1 = Me; 3b, R 1 = n -Pr; 3c, R 1 = n -Hep; 3d, R 1 = CH 2 CH 2 Ph; 3e, R 1 = i -Pr] were successfully rearranged to their respective branched amides [H 2 C CHCH(R 1 )NHC(O)CCl 3: 4a − e ] using 5 mol % 2b as catalyst. Isolated yields ranged from a low of 33% for the bulky 4e to a high of 91% for 4a .
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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 | 0.001 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| 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".