Beschreibung:
<jats:title>Abstract</jats:title>
<jats:p>Two <jats:italic>cis</jats:italic>-dioxovanadium(V) complexes and three monooxovanadium(V) complexes with different coordination numbers and ligand spheres, serving as model complexes for vanadium haloperoxidases, were studied by <jats:sup>51</jats:sup>V solid-state NMR spectroscopy. The most important <jats:sup>51</jats:sup>V solid-state NMR parameters (quadrupolar coupling constant <jats:italic>C</jats:italic>
<jats:sub>
<jats:italic>Q</jats:italic>
</jats:sub>, asymmetry of the EFG tensor <jats:italic>η</jats:italic>
<jats:sub>
<jats:italic>Q</jats:italic>
</jats:sub>, isotropic chemical shift <jats:italic>δ</jats:italic>
<jats:sub>
<jats:italic>iso</jats:italic>
</jats:sub>, chemical shift anisotropy <jats:italic>δ</jats:italic>
<jats:sub>
<jats:italic>σ</jats:italic>
</jats:sub>, asymmetry of the CSA tensor <jats:italic>η</jats:italic>
<jats:sub>
<jats:italic>σ</jats:italic>
</jats:sub> and the Euler angles <jats:italic>α</jats:italic>, <jats:italic>β</jats:italic> and <jats:italic>γ</jats:italic>) describing the quadrupolar and chemical shift anisotropy interactions were determined theoretically with DFT methods employing the B3LYP functional and experimentally using genetic fitting algorithms. Calculations of <jats:italic>δ</jats:italic>
<jats:sub>
<jats:italic>iso</jats:italic>
</jats:sub> values were treated with different referencing values of VOCl<jats:sub>3</jats:sub> computed with different-sized basis sets using the “counterpoise method”. The calculated <jats:italic>C</jats:italic>
<jats:sub>
<jats:italic>Q</jats:italic>
</jats:sub> values were discussed in terms of the quadrupolar moment <jats:italic>Q</jats:italic>. Absolute tensor orientations of CSA and EFG tensors were computed by DFT. These orientations were found to correlate to structural features of the model complexes.</jats:p>