Synthesis and characterization of three new fluorovanadate complexes: N(C2H5)4+[VOF4]−, N(CH3)4+[VOF3Cl]−, N(C4H9)4+[VOF3Br]− and theoretical calculations of VOF4−, VOF3Cl− and VOF3Br− ions

The reaction of VOF3 with (C2H5)4NF, (CH3)4NCl and (C4H9)4NBr salts in anhydrous CH3CN produced new complexes with the anion general formula [VOF3X]− in that (X = F−, Cl−, Br−). These were characterized by elemental analysis, IR, UV/Visible and 19F NMR spectroscopy. The optimized geometries and frequencies of the stationary point are calculated at the B3LYP/6-311G level of theory. Theoretical results showed that the VX (X = F, Cl, Br) bond length values for the [VOF3X]− in compounds 1–3 are 1.8247, 2.4031 and 2.5595 Å, respectively. Also, the VF5 bond length values in [VOF3X]− are 1.824, 1.812 and 1.802 Å, respectively. These results reveal that the bond order for VX bonds decrease from compounds 1 to 3, while for VF5 bonds, the bond orders increase. It can be concluded that the decrease of VX bonds lengths and the increase of VF5 bond lengths in compounds 1–3 result from the increase of the hyperconjugation from compounds 1 to 3. Harmonic vibrational frequencies and infrared intensities for VOF4−, VOF3Cl− and VOF3Br− are studied by means of theoretical and experimental methods. The calculated frequencies are in reasonable agreement with the experiment values. These data can be used in models of phosphoryl transfer enzymes because vanadate can often bind to phosphoryl transfer enzymes to form a trigonal-bipyramidal structure at the active site.