Exploring the influence of H-bonding and ligand constraints on thiolate ligated non-heme iron mediated dioxygen activation.

ABSTRACT: Converting triplet dioxygen into a powerful oxidant is fundamentally important to life. The study reported herein quantitatively examines the formation of a well-characterized, reactive, O₂-derived thiolate ligated Fe^III-superoxo using low-temperature stopped-flow kinetics. Comparison of the kinetic barriers to the formation of this species via two routes, involving either the addition of (a) O₂ to [Fe^II(S₂ ^Me2N₃(Pr,Pr))] (1) or (b) superoxide to [Fe^III(S₂ ^Me2N₃(Pr,Pr))]⁺ (3) is shown to provide insight into the mechanism of O₂ activation. Route (b) was shown to be significantly slower, and the kinetic barrier 14.9 kJ mol^-1 higher

SUBMITTER: Lundahl MN 

PROVIDER: S-EPMC11325341 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature