chlorate complex 6a resulted in Cl-O bond homolysis to generate a Mn(IV) oxo compound 7; in contrast, flash photolysis of Mn(III) perchlorate complex 6b resulted in Cl-O bond heterolysis to generate a Mn(V) oxo complex 8. Similar photochemically promoted O-X cleavage to generate Mn oxo complexes was described by Suslick and co-workers in the context of porphyrin-supported Mn nitrite and nitrate complexes, and Zhang and co-workers have described photogeneration of Mn oxo complexes from µ-oxo dimanganese precursors. Figure 3. (a) Photolysis of Mn chlorate 6a affords Mn(IV) oxo 7 via Cl-O homolysis whereas photolysis of Mn perchlorate 6b affords Mn(V) oxo 7 via Cl-O homolysis. (b) Corresponding Mn nitrenoid photochemistry would be enabled if control over hetero-and homolytic N-X cleavage processes could be achieved in haloamide complexes.