SEARCH

SEARCH BY CITATION

Keywords:

  • density functional calculations;
  • dioxygen ligands;
  • high oxidation states;
  • iridium;
  • matrix isolation
Thumbnail image of graphical abstract

A state of eight: Iridium atoms insert into dioxygen to form iridium dioxide molecules in solid noble-gas matrices. Annealing allows formation of the iridium dioxide superoxide complex [(η1-O2)IrO2], which isomerizes under IR irradiation to the iridium dioxide peroxide complex [(η2-O2)IrO2]. These complexes photochemically rearrange to the more stable iridium tetroxide molecule with an iridium oxidation state of +VIII (see scheme; Ir black, O red).