A Reactive, Photogenerated High-Spin (S = 2) Fe^IV(O) Complex via O₂ Activation.

ABSTRACT: Addition of dioxygen at low temperature to the non-heme ferrous complex Fe^II(Me₃TACN)((OSi^Ph2)₂O) (1) in 2-MeTHF produces a peroxo-bridged diferric complex Fe₂^III(μ-O₂)(Me₃TACN)₂((OSi^Ph2)₂O)₂ (2), which was characterized by UV-vis, resonance Raman, and variable field Mössbauer spectroscopies. Illumination of a frozen solution of 2 in THF with white light leads to homolytic O-O bond cleavage and generation of a Fe^IV(O) complex 4 (ν(Fe=O) = 818 cm^-1; δ = 0.22 mm s^-1, ΔE_Q = 0.23 mm s^-1). Variable field Mössbauer spectroscopy measurements show that 4 is a rare example

SUBMITTER: Gordon JB 

PROVIDER: S-EPMC9109941 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature