Nitrosyl complexes of vanadium, niobium, tantalum, tungsten, and iron
Bibliographic record
Abstract
Treatment of V(CO)₅(NO) with trimpsi (trimpsi = BuSi(CH₂PMe₂)₃), followed by heating in THF, generates (trimpsi)V(CO)₂NO in moderate yields. (trimpsi)V(CO)₂NO has been studied by X-ray crystallography, ⁵¹V{¹H} NMR spectroscopy, and cyclic voltammetry. (trimpsi)V(CO)₂NO can be oxidised by the reaction with [Cp₂Fe] [BF₄], generating [(trimpsi) V(CO)₂NO] [BF₄]. Treatment of (trimpsi) V(CO)₂NO with one equiv of PhICl₂, Br₂, or I₂, or two equiv of C1NO, generates (trimpsi)VX₂ (NO) (X = CI, Br, I) in good yields. Treatment of (trimpsi)M(CO)₂NO (M = Nb, Ta) with I₂, followed by addition of excess PMe₃, provides (trimpsi)MI₂(NO)(PMe₃) in low to moderate yields. The reaction between (trimpsi)M(CO)₂NO (M - Nb, Ta) with one equiv of C1NO provides (trimpsi)M(NO) ₂Cl. These two complexes are thermally sensitive and have only been characterised by low-temperature IR and NMR spectroscopies. Treatment of (trimpsi)VCl₂ (NO) with p-toluic acid and Proton Sponge provides (trimpsi)V(O₂CPh-4-Me)₂(NO) in moderate yield. Alternatively, treatment of (trimpsi) V(CO)₂NO with benzoyl peroxide also generates a carboxylate complex, namely (trimpsi)V(O₂CPh)₂(NO). The reaction between (trimpsi)VCl₂(NO) and 0.5 equiv of MgR₂x(dioxane) (R = CH₂SiMe₃, CH₂CMe₃, Me) forms (trimpsi)V(R)Cl(NO) in good yields. Several attempts to form complexes of the type (trimpsi)VR₂(NO) have been unsuccessful. Treatment of [V(NO)₃Cl2][sub n] with excess THF generates mer-(THF)₃VCl₂(NO) in good yield. The reaction of mer-(THF)₃VCl₂(NO) with excess MeCN generates fac- (MeCN)₃VCl₂(NO). Both complexes have been characterised by X-ray crystallography. The reaction of VCI₄ with NO has been found to generate [NO][VCl₅] and VCI₃. [NO][VCl₅] can also be formed by the reaction of VC1₄ and C1NO. Treatment of [NO][VCl₅] with excess [NEt₃CH₂Ph][Cl] generates [NEt₃CH₂Ph]₂[VCl₆] in moderate yield, while exposure of a DME solution of [NO][VCl₅] to air generates (DME)VC1₂(O)(μ-O)V(O)C1₂(DME). The reaction between Fe(NO)₃Cl and [Ag][X] (X = BF₄, PF₆) forms Fe(NO)₃(η¹-X) in moderate yields. Alternatively, Fe(NO)₃( η¹-X) can also be formed by the action of [NO][X] upon Fe powder. Fe(NO)₃( η¹-BF₄) has been characterised by X-ray crystallography. During the course of this research [Fe(NO)₃(EtCN)][PF₆] and [Fe(NO)₃(μ-PO₂F₂)Fe(NO)₃][PF₆] have also been isolated and structurally characterised. The iron trinitrosyl complexes exhibit bent nitrosyl linkages and a molecular orbital rationale is given to explain these metrical parameters. The solid-state molecular structure of another trinitrosyl complex, namely fac-W(NO)₃C1₃, was also determined. fac-W(NO)₃Cl₃ exhibits linear nitrosyl ligands, and a rationale is provided to explain the difference between the iron and tungsten cases.
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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 | 0.000 | 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) | 0.000 | 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 teacher head, 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".