(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 center dot center dot center dot N coupling. It is proposed that the resulting manganese(III) mu-diazene species decomposes via internal redox to give N-2 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).