Electronic Structure and Reactivity of Dioxygen-Derived Aliphatic Thiolate-Ligated Fe-Peroxo and Fe(IV) Oxo Compounds.

ABSTRACT: Herein, we examine the electronic and geometric structural properties of O₂-derived aliphatic thiolate-ligated Fe-peroxo, Fe-hydroxo, and Fe(IV) oxo compounds. The latter cleaves strong C-H bonds (96 kcal mol^-1) on par with the valine C-H bond cleaved by isopencillin N synthase (IPNS). Stopped-flow kinetics studies indicate that the barrier to O₂ binding to [Fe^II(S^Me2N₄(tren))]⁺ (3) is extremely low (E_a = 36(2) kJ mol^-1), as theoretically predicted for IPNS. Dioxygen binding to 3 is shown to be reversible, and a superoxo intermediate, [Fe^III(S^Me2N₄(tren))(O₂)]⁺ (6), forms in the first 25 ms of the reaction at -

SUBMITTER: Dedushko MA 

PROVIDER: S-EPMC9281583 | biostudies-literature | 2022 May

REPOSITORIES: biostudies-literature