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

Title Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by O solid-state NMR and density functional theory.
Authors R. Gupta; J. Stringer; J. Struppe; D. Rehder; T. Polenova
Journal Solid State Nucl Magn Reson
DOI 10.1016/j.ssnmr.2018.02.001
Abstract

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 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 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.

Citation R. Gupta; J. Stringer; J. Struppe; D. Rehder; T. Polenova.Direct detection and characterization of bioinorganic peroxo moieties in a vanadium complex by O solid-state NMR and density functional theory.. Solid State Nucl Magn Reson. 2018;91:1520. doi:10.1016/j.ssnmr.2018.02.001

Related Elements

Vanadium

23 V 50.941500000 Vanadium

See more Vanadium products. Vanadium (atomic symbol: V, atomic number: 23) is a Block D, Group 5, Period 4 element with an atomic weight of 50.9415. Vanadium Bohr ModelThe number of electrons in each of Vanadium's shells is 2, 8, 11, 2 and its electron configuration is [Ar] 3d3 4s2. The vanadium atom has a radius of 134 pm and a Van der Waals radius of 179 pm. Vanadium was discovered by Andres Manuel del Rio in 1801 and first isolated by Nils Gabriel Sefström in 1830. In its elemental form, vanadium has a bluish-silver appearance. Elemental VanadiumIt is a hard, ductile transition metal that is primarily used as a steel additive and in alloys such as Titanium-6AL-4V, which is composed of titanium, aluminum, and vanadium and is the most common titanium alloy commercially produced. Vanadium is found in fossil fuel deposits and 65 different minerals. Vanadium is not found free in nature; however, once isolated it forms an oxide layer that stabilizes the free metal against further oxidation. Vanadium was named after the word "Vanadis" meaning goddess of beauty in Scandinavian mythology.

Related Forms & Applications

Organometallics
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