Nitrene Photochemistry of Manganese N-Haloamides

Here we report the synthesis and nitrene transfer photochemistry of Mn(III) N-haloamide complexes. Photolysis results in both C–H bond amination and olefinic aziridination products. Low-temperature spectroscopy indicates halogen-dependent photoreactivity: Photolysis of N-chloroamides cleaves the Mn–N bond to generate Mn(II) and amidyl radical species; in contrast, photolysis of N-iodoamides proceeds via N–I cleavage yielding a formally Mn(IV) nitrenoid.