Different Modes of Reactivity of Cp*W(NO)(alkyl)(η<sup>3</sup>-allyl) Complexes with Cyclic Amines: The Influence of the Allyl Ligands
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Bibliographic record
Abstract
Metathesis reactions between Cp*W(NO)(CH 2 EMe 3 )Cl (E = C or Si) and a variety of bis(allyl)magnesium reagents lead to the formation of 18e Cp*W(NO)(alkyl)(η 3 -allyl) complexes. The compounds Cp*W(NO)(CH 2 CMe 3 )(η 3 -CH 2 CHCMe 2 ) ( 1 ), Cp*W(NO)(CH 2 CMe 3 )(η 3 -CH 2 CMeCH 2 ) ( 2 ), Cp*W(NO)(CH 2 CMe 3 )(η 3 -CH 2 CHCHMe) ( 3 ), Cp*W(NO)(CH 2 CMe 3 )(η 3 -CH 2 CHCHPh) ( 4 ), Cp*W(NO)(CH 2 SiMe 3 )(η 3 -CH 2 CHCHMe) ( 5 ), and Cp*W(NO)(CH 2 CMe 3 )(η 3 -CH 2 CHCH 2 ) ( 6 ) have thus been synthesized in moderate yields. The solid-state molecular structures of 3, 4, 5, and 6 feature σ−π distorted allyl ligands in the endo conformation. Complex 1 effects the concurrent N−H and α-C−H activations of pyrrolidine and piperidine under ambient conditions and forms the alkyl amido complexes Cp*W(NO)(CH 2 CMe 3 )(NC 4 H 7 -2-CMe 2 CH═CH 2 ) ( 7 ) and Cp*W(NO)(CH 2 CMe 3 )(NC 5 H 9 -2-CMe 2 CH═CH 2 ) ( 8 ), respectively. Complexes 2 − 5 react with pyrrolidine in a similar manner, but the reaction of 3 to produce Cp*W(NO)(CH 2 CMe 3 )(NC 4 H 7 -2-CH 2 CMe═CH 2 ) ( 10 ) is not as clean since 3 is thermally unstable at 20 °C. Unfortunately, the concurrent N−H and α-C−H activation transformation encompasses only a very limited range of substrates, namely cyclic amines. Complex 6, which contains an unsubstituted allyl ligand, exhibits a unique mode of reactivity with pyrrolidine and piperidine, incorporating 2 equiv of the amines and forming Cp*W(NO)(NC 4 H 8 )(CHMeCH 2 NC 4 H 8 ) ( 13 ) and Cp*W(NO)(NC 5 H 10 )(CHMeCH 2 NC 5 H 10 ) ( 14 ), respectively. Plausible mechanisms are suggested to account for the different modes of reactivity of the Cp*W(NO)(alkyl)(η 3 -allyl) compounds with the cyclic amines. All new complexes have been characterized by conventional spectroscopic methods, and representative compounds have also been subjected to single-crystal X-ray crystallographic analyses.
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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) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 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 it