New oxidovanadium(V) complexes of the cation [VO]3+: Synthesis, structural characterization and DFT studies

5-Tert-butyl-(3-(1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylimino)methyl)-2-hydroxybenzaldehyde (L1), (4-tert-butyl-2-(1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylimino)methyl)-6-(dimethoxymethyl) phenol (L2) and (2-(1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylimino)methyl)-6-methoxyphenol (L3), react with vanadyl acetylacetonate to give the vanadium(V) complexes [VO(L1-3H+)]2·dmso, [VO(L2-3H+)]2 and [VO(L3-3H+)]2·dmso. All complexes present the vanadium(V) center as the less common [VO]3+ cation. The structural features of the title compounds, specially the occurrence of supramolecular assemblies supported by bifurcated and trifurcated hydrogen bonding are discussed, as well as DFT studies and HOMO–LUMO energy gaps. Calculated spatial maps of the Fukui functions, f+(r) and f−(r), are also presented and discussed.

The dimeric complexes [VO(L1-3H+)]2·dmso, [VO(L2-3H+)]2 and [VO(L3-3H+)]2·dmso were obtained through reaction of the organic ligands L1, L2 and L3 with VO(acac)2. The vanadium(V) centers occur in all complexes as [VO]3+ cation. Bifurcated and trifurcated hydrogen bondings support the supramolecular assemblies of the L1 and L3 complexes. DFT studies and HOMO–LUMO energy gaps, as well as spatial maps of the Fukui functions, f+(r) and f−(r), are also presented and discussed.Figure optionsDownload as PowerPoint slideHighlights
► Synthesis and structural characterization of vanadium(V) complexes in form of [VO]3+ cations.
► Occurrence of bifurcated and trifurcated secondary hydrogen bonds supporting supramolecular structures.
► DFT studies, as well as HOMO–LUMO drawings and energy gaps calculations.
► Discussion of the spatial maps of the Fukui functions, f+(r) and f−(r) for the title complexes.