Reactivity of (trimpsi)V(NO)X<sub>2</sub>Complexes (X = Cl, Br, I; trimpsi =<sup>t</sup>BuSi(CH<sub>2</sub>PMe<sub>2</sub>)<sub>3</sub>). Synthesis of the First Group 5 Alkyl Nitrosyls
Bibliographic record
Abstract
Treatment of (trimpsi)V(NO)Cl 2 (trimpsi = t BuSi(CH 2 PMe 2 ) 3 ) in NEt 3 with 2 equiv each of p -toluic acid and Proton Sponge affords lemon yellow (trimpsi)V(NO)(η 1 -O 2 C-4-C 6 H 4 Me) 2 ( 1 ) in 47% isolated yield. Similarly, reaction of (trimpsi)V(NO)Cl 2 with 2 equiv of AgOTf in CH 2 Cl 2 provides lemon yellow (trimpsi)V(NO)(OTf) 2 ( 2 ) in a comparable yield. Alternatively, 2 can be obtained directly in 40% yield by treating CH 2 Cl 2 solutions of (trimpsi)V(CO) 2 (NO) at −60 °C with 2 equiv of AgOTf. Likewise, both benzoyl peroxide and diphenyl disulfide are capable of oxidizing (trimpsi)V(CO) 2 (NO) under similar conditions to form (trimpsi)V(NO)X 2 -type complexes, namely (trimpsi)V(NO)(O 2 CPh) 2 ( 3 ) and (trimpsi)V(NO)(SPh) 2 ( 4 ), respectively. The reactions of (trimpsi)V(NO)X 2 (X = Cl, Br) with Mg(CH 2 SiMe 3 ) 2 · x (dioxane) (either 0.5 equiv or an excess) in THF afford the orange-red alkyl complexes (trimpsi)V(NO)(CH 2 SiMe 3 )X (X = Cl ( 5 ), Br ( 6 )) in reasonable yields. Other members of this family of complexes such as (trimpsi)V(NO)(CH 2 CMe 3 )Cl ( 7 ) and (trimpsi)V(NO)(Me)Cl ( 8 ) can also be obtained by employing similar metathetical methodology, but all attempts to synthesize (trimpsi)V(NO)(alkyl) 2 complexes have to date been unsuccessful. All new complexes have been fully characterized by standard methods, and the solid-state molecular structures of 1 ·1.5C 6 H 5 Me and 5 ·2C 4 H 8 O have been established by single-crystal X-ray diffraction 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".