Thermal Chemistry of Cp*W(NO)(H)(η<sup>3</sup>-allyl) Complexes
Bibliographic record
Abstract
The thermal properties of Cp*W(NO)(H)(η 3 -CH 2 CHCMe 2 ) ( 1 ), Cp*W(NO)(H)(η 3 -CH 2 CHCHPh) ( 2 ), and Cp*W(NO)(H)(η 3 -CH 2 CHCHMe) ( 3 ) (Cp* = η 5 -C 5 Me 5 ) have been investigated. Thermolyses of 1 – 3 in n -pentane lead to the loss of the original allyl ligand and the formation of the same mixture of isomeric products, namely, Cp*W(NO)(H)(η 3 -CH 2 CHCHEt) ( 4a ) and Cp*W(NO)(H)(η 3 -MeCHCHCHMe) ( 4b ) and their coordination isomers. Similarly, 1 reacts with cyclohexane and n -heptane to form Cp*W(NO)(H)(η 3 -C 6 H 9 ) and isomers of Cp*W(NO)(H)(η 3 -C 7 H 13 ), respectively. It is likely that complexes 1 – 3 first effect the selective, single-terminal C–H activation of the linear alkanes, but the first-formed products are thermally unstable and undergo two additional successive C–H activations to form the final allyl complexes. Consistent with this view is the fact that a bis(alkyl) intermediate complex can be trapped with N -methylmorpholine. Thus, the thermolysis of 1 in N -methylmorpholine affords a single organometallic complex, Cp*W(NO)(η 2 -CH 2 NC 4 H 8 O)(η 1 -CH 2 CH 2 CHMe 2 ) ( 7 ). Complexes 2 and 3 react with N -methylmorpholine in an identical manner. Finally, 1 effects the multiple C–H activations of 1-chloropropane and 1-chlorobutane and forms the corresponding Cp*W(NO)(Cl)(η 3 -allyl) complexes. All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most 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".