Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by O-17 solid-state NMR and density functional theory

作者：Gupta Rupal; Stringer John; Struppe Jochem; Rehder Dieter; Polenova Tatyana^*

来源：Solid State Nuclear Magnetic Resonance, 2018, 91: 15-20.

DOI：10.1016/j.ssnmr.2018.02.001

• O-17 solid state NMR
• Density functional theory calculations
• Peroxido ligand
• Reactive intermediates

Electronic and structural properties of short-lived metal-peroxido complexes, which are key intermediates in many enzymatic reactions, are not fully understood. While detected in various enzymes, their catalytic properties remain elusive because of their transient nature, making them difficult to study spectroscopically. We integrated O-17 solid-state NMR and density functional theory (DFT) to directly detect and characterize the peroxido ligand in a bioinorganic V(V) complex mimicking intermediates non-heme vanadium haloperoxidases. O-17 chemical shift and quadrupolar tensors, measured by solid-state NMR spectroscopy, probe the electronic structure of the peroxido ligand and its interaction with the metal. DFT analysis reveals the unusually large chemical shift anisotropy arising from the metal orbitals contributing towards the magnetic shielding of the ligand. The results illustrate the power of an integrated approach for studies of oxygen centers in enzyme reaction intermediates.

• 出版日期2018-7