Demetalation of Fe(III) microperoxidase-8 (MP8) by anhydrous HF gives
metal-free MP8. a convenient starting material for a wide variety of m
etal-substituted MP8 derivatives, including Mn(III)MP8. Mn(III)MP8 was
produced by treatment of metal-free MP8 with manganous acetate in aer
ated aqueous solution; it was characterized by mass spectrometry and U
V-visible absorption spectroscopy. Resonance Raman spectra suggest tha
t Mn(III)MP8 contains histidine and water axial ligands at neutral pH.
The Mn(IV)=O derivative is readily prepared by oxidation of Mn(III))M
P8 with hydrogen peroxide or Ru(bpy)3(3+) (bpy = 2,2'-bipyridine).