Spectroscopic Characterization of a Hydroperoxo–Heme Intermediate: Conversion of a Side-On Peroxo to an End-On Hydroperoxo Complex


  • This work was financially supported by Grants-in-Aid for Scientific Research (S) (no. 17105003, YN), for Young Scientists (B) (no. 27150173, JGL) from JSPS, on Priority Areas (no. 19027044, YN), Innovative Areas (no. 20200050, JGL) from MEXT; and by the Elemental Science and Technology Project from MEXT. The 430 nm laser was set up by Dr. Ken’ichi Nakagawa, The University of Electro-Communications (Japan).


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Modeling job: Protonation of a closed seven-coordinate side-on heme peroxide can switch its spin state from high- to low-spin and convert the η2 binding fashion into a monodentate configuration to afford the corresponding hydroperoxide (see scheme). The end-on low-spin ferric hydroperoxo–heme species bear a covalently appended axial imidazole ligand and are easily prepared.