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- W2898099805 abstract "Reaction of vanadium(V) oxide trifluoride (VOF3) and the new “naked” fluoride reagent [(LDipp)H][F] (LDipp = 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene) leads to the isolation of [(LDipp)H][VOF4] (1) where the long sought discrete [VOF4]− anion was finally obtained. The neutral [(LDipp)VOF3] (2) complex was synthesized by a similar reaction between VOF3 and bulky N-heterocyclic carbene (NHC) ligand LDipp. In this context, we analyzed, by means of DFT calculations, intermolecular interactions between [(LDipp)VOF3] (2) complexes in the crystal structure and realized that these interactions have a significant effect on the V–Ftrans bond length. We further scrutinized ligand bonding within [(LDipp)VOF3] (2) and related complexes, because, in this kind of complexes, a rather short distance between CNHC and cis-halogen atoms has spurred some discussion about the type of interactions between them. We provide evidence of a minute π back-bonding into NHC ligands, which is larger for chloride [(NHC)VOCl3] than fluoride [(NHC)VOF3] complexes, although the fluoride ions are, counterintuitively and to a larger degree, involved in back-bonding than chloride ions. The influence of π back-bonding on V–Ftrans and V–Fcis bond lengths was also rationalized. Finally, the hydrolysis of [(LDipp)VOF3] (2) product was studied and [(LDipp)H][VO2F2] (3) salt was obtained and characterized as the most stable product in this system." @default.
- W2898099805 created "2018-11-02" @default.
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- W2898099805 date "2018-10-24" @default.
- W2898099805 modified "2023-10-18" @default.
- W2898099805 title "Reactivity of VOF<sub>3</sub> with N-Heterocyclic Carbene and Imidazolium Fluoride: Analysis of Ligand–VOF<sub>3</sub> Bonding with Evidence of a Minute π Back-Donation of Fluoride" @default.
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- W2898099805 doi "https://doi.org/10.1021/acs.inorgchem.8b02377" @default.
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