Dismantling of Vinyl Ethers by Pentanuclear [(<i>i</i>Pr<sub>3</sub>P)Ni]<sub>5</sub>H<sub>6</sub>: Facile Cooperative C−O, C−C and C−H Activation Pathways
Bibliographic record
Abstract
Abstract The [( i Pr 3 P)Ni] 5 H 6 cluster ( 1 ) and H 2 C=CHO t Bu react at room temperature to form the new pentanuclear NiH carbide [( i Pr 3 P)Ni] 5 H 4 (C)(CO) ( 3 ), along with an equivalent of isobutylene. This transformation requires the activation of multiple unreactive bonds, including C−H, C−C, and C(sp 3 )−O bond cleavage. Analysis of the reaction mixture by 1 H NMR revealed the production of two additional paramagnetic species, assigned as [( i Pr 3 P)Ni] 4 H 4 (C‐CH 3 )NiO t Bu ( 4 a ) and [( i Pr 3 P)Ni] 4 H 4 (C‐CH 2 O t Bu)NiO t Bu ( 5 a ), which arise from C(sp 2 )−O bond cleavage and CH bond rearrangements. The reaction of 1 with H 2 C=CHOSiMe 2 CH 2 Ph produced the isolable 4 a analogue [( i Pr 3 P) 4 Ni 5 ]H 4 (CCH 3 )(OSiMe 2 CH 2 Ph) ( 4 c ). An isolable analogue of 5 a was obtained from the reaction of 1 with H 2 C=CHOAd (Ad=1‐admantyl), which produced [( i Pr 3 P) 4 Ni 5 ]H 4 (CCH 2 OAd)(OAd) ( 5 d ). The utilization of both cluster faces and vertices for bonding substrate fragments in these transformations demonstrates the remarkable flexibility of the robust Ni 5 H 4 core in the cooperative activation of multiple C−O, C−C and C−H bonds.
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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) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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".