DFT Calculations of 51V Solid-State NMR Parameters of Vanadium(V) Model Complexes

Abstract

Abstract Two cis-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 51V solid-state NMR spectroscopy. The most important 51V solid-state NMR parameters (quadrupolar coupling constant C Q , asymmetry of the EFG tensor η Q , isotropic chemical shift δ iso , chemical shift anisotropy δ σ , asymmetry of the CSA tensor η σ and the Euler angles α, β and γ) 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 δ iso values were treated with different referencing values of VOCl3 computed with different-sized basis sets using the “counterpoise method”. The calculated C Q values were discussed in terms of the quadrupolar moment Q. 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.