Laser flash photolysis study of azides derived from Cr(iii) and Mn(iii) salen complexes

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.