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Keywords:

  • bioinorganic chemistry;
  • enzyme models;
  • heme proteins;
  • iron;
  • O[BOND]O activation
Thumbnail image of graphical abstract

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.