Reactivity of an Fe^IV-Oxo Complex with Protons and Oxidants.

ABSTRACT: High-valent Fe-OH species are often invoked as key intermediates but have only been observed in Compound II of cytochrome P450s. To further address the properties of non-heme Fe^IV-OH complexes, we demonstrate the reversible protonation of a synthetic Fe^IV-oxo species containing a tris-urea tripodal ligand. The same protonated Fe^IV-oxo species can be prepared via oxidation, suggesting that a putative Fe^V-oxo species was initially generated. Computational, Mössbauer, XAS, and NRVS studies indicate that protonation of the Fe^IV-oxo complex most likely occurs on the tripodal ligand, which undergoes a structural change that results in the formation of a new intramolecular H-bond with the oxido ligand that aids in stabilizing the protonated a

SUBMITTER: Hill EA 

PROVIDER: S-EPMC5110122 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature