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

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 ¹⁷O 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. ¹⁷O 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 anisotr

SUBMITTER: Gupta R 

PROVIDER: S-EPMC6267778 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature