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Keywords:

  • hydrogen-atom transfer;
  • ligand effects;
  • manganese;
  • metalloenzymes;
  • porphyrinoids
Thumbnail image of graphical abstract

Runaway reactivity: A manganese(V)–oxo porphyrinoid complex displays an unprecedented increase in reaction rate for a hydrogen-atom abstraction upon addition of anionic axial ligands (X=F and CN; see scheme). Density functional theory calculations are in excellent agreement with experiment, and provide insight into the origins of these remarkable axial ligand effects.