Functionalization of Methane Initiated by Cp*W(NO)(CH<sub>2</sub>CMe<sub>3</sub>)(η<sup>3</sup>-CH<sub>2</sub>CHCMe<sub>2</sub>)
Bibliographic record
Abstract
Cp*W(NO)(CH 2 CMe 3 )(η 3 -CH 2 CHCMe 2 ) ( 1 ) initiates a stepwise conversion of methane into unsymmetrical unsaturated ketones. The first step involves the activation of methane by 1 in cyclohexane to form Cp*W(NO)(CH 3 )(η 3 -CH 2 CHCMe 2 ) ( 2 ) in good yield as a mixture of two isomers that differ with respect to the exo/endo orientation of their allyl ligands. Subsequent exposure of a cyclohexane solution of 2 to 500 psig of CO pressure and 75 °C for 3 h results in the 1,1-insertion of CO into the W–CH 3 linkage of 2 and formation of the yellow acyl complex Cp*W(NO)(C(═O)CH 3 )(η 3 -CH 2 CHCMe 2 ) ( 5 ). Additional carbonylation of 2 can be effected by maintaining the cyclohexane solution at 750 psig of CO pressure and 75 °C for 3 days, a process that results in the formation of the isomeric η 2 -unsaturated-ketone complexes Cp*W(NO)(CO)(η 2 -Me 2 C═CHCH 2 C(O)CH 3 ) ( 6a ) and Cp*W(NO)(CO)(η 2 -H 2 C═CHCMe 2 C(O)CH 3 ) ( 6b ) in a 60:40 ratio. Finally, exposure of 2 to CO under more forcing conditions (1000 psig at 170 °C for 3 days) produces Cp*W(NO)(CO) 2 ( 8 ) and the isomeric β,γ-unsaturated ketones 5-methylhex-4-en-2-one ( 9a ), 3,3-dimethylpent-4-en-2-one ( 9b ), and trans -5-methylhex-3-en-2-one ( 9c ) in a 92:5:3 ratio. Similarly, maintaining an Et 2 O solution of 1 at 1000 psig of CO and 170 °C for 3 days results in the complete conversion of 1 into 8 and liberates 2,2,7-trimethyloct-6-en-4-one ( 10 ). The final organometallic complex, 8, can be reconverted into the initial reactant 1 via Cp*W(NO)Cl 2, which in turn is cleanly obtained by treatment of 8 with PCl 5 . All new compounds have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of five of them have been established by single-crystal X-ray crystallographic analyses.
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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 | 0.004 |
| Meta-epidemiology (narrow) | 0.002 | 0.002 |
| Meta-epidemiology (broad) | 0.002 | 0.001 |
| Bibliometrics | 0.002 | 0.006 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.002 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.002 | 0.001 |
| Insufficient payload (model declined to judge) | 0.001 | 0.002 |
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; both teacher heads agree on what is shown here.
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".