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.

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Can a neutral ligand bond to a metal center of a square pyramidal oxohalido anion at the available sixth octahedral position? Crystal structures of some compounds indeed suggest that ligands, such as THF, pyridine, H 2 O, NH 3 , and CH 3 CN, can interact with the central metal atom, because they are oriented with their heteroatom toward the metal center with distances being within the bonding range. However, this assumption that is based on chemical intuition is wrong. In-depth analysis of interactions between ligands and oxohalido anions (e.g., VOX 4 – , NbOCl 4 – ) reveals that the bonding of a neutral ligand is almost entirely due to electrostatic interactions between the H atoms of a ligand and halido atoms of an anion. Furthermore, ab initio calculations indicate that the ligand–VOF 4 – interactions represent only about one-quarter of the total binding of the ligand within the crystal structure, whereas the remaining binding is due to crystal packing effects. The current study therefore shows that relying solely on the structural aspects of solved crystal structures, such as ligand orientation and bond distances, can lead to the wrong interpretation of the chemical bonding.