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 machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 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) | 0.002 | 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 source (direct Gemma or distilled Codex), 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".