Formation of a Reactive, Alkyl Thiolate-Ligated Fe^III-Superoxo Intermediate Derived from Dioxygen.

ABSTRACT: Herein, we describe an alkyl thiolate-ligated iron complex that reacts with dioxygen to form an unprecedented example of an iron superoxo (O₂^•-) intermediate, [Fe^III(S₂^Me2N₃(Pr,Pr))(O₂)] (4), which is capable of cleaving strong C-H bonds. A cysteinate-ligated iron superoxo intermediate is proposed to play a key role in the biosynthesis of β-lactam antibiotics by isopenicillin N-synthase (IPNS). Superoxo 4 converts to a metastable putative Fe(III)-OOH intermediate, at rates that are dependent on the C-H bond strength of the H atom donor, with a kinetic isotope effect ( k_H/ k_D = 4.8) comparable to that of IPNS ( k_H/ k_D = 5.6). The bond dissociation energy of the C-H bonds

SUBMITTER: Blakely MN 

PROVIDER: S-EPMC6942688 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature