Activation of Dioxygen by a Mononuclear Nonheme Iron Complex: Sequential Peroxo, Oxo, and Hydroxo Intermediates.

ABSTRACT: The activation of dioxygen by Fe^II(Me₃TACN)(S₂SiMe₂) (1) is reported. Reaction of 1 with O₂ at -135 °C in 2-MeTHF generates a thiolate-ligated (peroxo)diiron complex Fe^III₂(O₂)(Me₃TACN)₂(S₂SiMe₂)₂ (2) that was characterized by UV-vis (λ_max = 300, 390, 530, 723 nm), Mössbauer (δ = 0.53, |ΔE_Q| = 0.76 mm s^-1), resonance Raman (RR) (ν(O-O) = 849 cm^-1), and X-ray absorption (XAS) spectroscopies. Complex 2 is distinct from the outer-sphere oxidation product 1^ox (UV-vis (λ_max = 435, 520, 600 nm), Mössbauer (δ = 0.45, |ΔE_Q| =

SUBMITTER: Gordon JB 

PROVIDER: S-EPMC7317638 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature