Abstract
Laser flash photolysis of (salen)Cr(III) and (salen)Mn(III) azides has shown that photodenitrogenation occurs through the intermediacy of triplet metal nitrenes. A minor competing pathway consisting in the formation of tetra-coordinated Mn(II) and Cr(II) fragments has also been observed. Both reaction paths are explained through two sorts of photocleavages centered on the azido apical ligand: (a) rupture of the N–N2 bond to form the coordinated triplet nitrene and (b) homolytic dissociation of the metal–N3 bond.
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