POCOP-Ligated Nickel Siloxide Complexes: Syntheses, Characterization, and Reactivities
Bibliographic record
Abstract
This report describes the reactivities of POCOP-type pincer complexes of nickel bearing a trimethylsiloxide ligand. The complex {κ P,κ C,κ P -2,6-(i-Pr 2 PO) 2 C 6 H 3 }Ni(OSiMe 3 ) ( 1-OSiMe 3 ) reacts with 2,4,6-Me 3 -C 6 H 2 OH (MesOH) to give the stable derivative 1-OMes, whereas the corresponding tert -butoxide derivative could not be prepared. Reaction of 1-OSiMe 3 and its aliphatic analogue {κ P,κ C,κ P -(i-Pr 2 POCH 2 ) 2 CH}Ni(OSiMe 3 ) ( 2-OSiMe 3 ) with Ph 3 SiOH led to facile formation of the corresponding protonolysis products 1-OSiPh 3 and 2-OSiPh 3 . Treating 1-OSiMe 3 or 2-OSiMe 3 with Me 3 SiN 3 gave the azide derivatives 1-N 3 or 2-N 3 in high isolated yields, whereas the analogous reactions with Me 3 SiCF 3 gave 2-CF 3 but not 1-CF 3 . These observations allow us to compare the reactivities of the Ni–OSiMe 3 moiety as a function of pincer ligand backbone. All new complexes have been characterized fully. The reaction of the azide derivatives with benzyl bromide led to the formation of benzyl azide and the corresponding bromo derivatives; 2-N 3 proved to be much more reactive than 1-N 3 . The analogous reactions with the trifluoromethyl derivatives are much more complicated and appear to convert PhCH 2 Br to Me-PhCF 3 and PhBr to PhF.
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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) | 0.001 | 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) | 0.018 | 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".