Facile N⋯N coupling of manganese(V) imido species

(Salen)manganese(V) nitrido species are activated by electrophiles such as trifluoroacetic anhydride (TFAA) or trifluoroacetic acid (TFA) to produce N ₂. Mechanistic studies suggest that the manganese(V) nitrido species first react with TFAA or TFA to produce an imido species, which then undergoes N⋯N coupling. It is proposed that the resulting manganese(III) μ-diazene species decomposes via internal redox to give N₂ and manganese(II). The manganese(II) species is then rapidly oxidized by manganese(V) imide to give manganese(III) and CF₃CONH₂ (for TFAA) or NH₃ (for TFA). © 2007 American Chemical Society.