Nuclear Resonance Vibrational Spectroscopic Definition of the Facial Triad Fe^IV═O Intermediate in Taurine Dioxygenase: Evaluation of Structural Contributions to Hydrogen Atom Abstraction.

ABSTRACT: The α-ketoglutarate (αKG)-dependent oxygenases catalyze a diverse range of chemical reactions using a common high-spin Fe^IV═O intermediate that, in most reactions, abstract a hydrogen atom from the substrate. Previously, the Fe^IV═O intermediate in the αKG-dependent halogenase SyrB2 was characterized by nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations, which demonstrated that it has a trigonal-pyramidal geometry with the scissile C-H bond of the substrate calculated to be perpendicular to the Fe-O bond. Here, we have used NRVS and DFT calculations to show that the Fe^IV═O complex in taurine dioxygenase (TauD), the αKG-dependent hydroxylase in which this intermediate was first characterized, also has a trigonal

SUBMITTER: Srnec M 

PROVIDER: S-EPMC7642179 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature