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 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 | 0.002 | 0.003 |
| Meta-epidemiology (narrow) | 0.003 | 0.003 |
| Meta-epidemiology (broad) | 0.005 | 0.004 |
| Bibliometrics | 0.001 | 0.005 |
| Science and technology studies | 0.002 | 0.002 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.005 | 0.002 |
| Research integrity | 0.002 | 0.002 |
| Insufficient payload (model declined to judge) | 0.001 | 0.001 |
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".