We present a density functional study of structures and reactivities of [VO(O
, a model peroxovanadium(V) complex with a biogenic ligand, and its potential use as catalyst in biomimetic oxidations of organic substrates. The mechanism of olefin epoxidation mediated by this complex is studied in detail for the gas-phase. In addition, structures and energetics of key intermediates in the catalytic cycle are simulated in solution using the Car-Parrinello molecular dynamics (CPMD) technique. The rate-limiting step is indicated to be oxo transfer from a peroxo moiety of the catalyst to the substrate. In a second part, the standard used for
V NMR spectroscopy, VOCl
, is modeled as neat liquid by means of CPMD simulations. According to preliminary results for the magnetic shieldings averaged along the trajectory, the
V nucleus is deshielded by ca. 40 ppm.