Using a simple metathesis approach, the triiron(II) tribromide complex Fe3Br3L (1) reacts with tetrabutylammonium azide to afford the monoazide dibromide analogue Fe-3(Br)(2)(N-3)L (2) in high yield. The inclusion of azide was confirmed by IR spectroscopy with a v(N-3) = 2082 cm(-1) as well as combustion analysis and X-ray crystallography. Heating 2 in the solid state results in the complete loss of the azide vibration in the IR spectra and the isolation of the olivegreen mononitride complex Fe-3(Br)(2)(N)L (3). Solution magnetic susceptibility measurements support that the trimetallic core within 2 is oxidized upon generation of 3 (5.07 vs 3.09 mu(B)). Absorption maxima in the UV-visible near-IR (NIR) spectra of 2 and 3 support the azide-to-nitride conversion, and a broad NIR absorption centered at 1117 nm is similar to that previously reported for the intervalence chargetransfer band for a mixed-valent nitridodiiron cluster. The cyclic voltammograms recorded for 3 are comparable to those of 1 with no reductive waves observed between similar to 0 and -2.5 V (vs Fc/Fc(+)), whereas a reversible one-electron redox process is observed for Fe-3(NH2)(3)L (4). These results suggest that intercluster cooperativity is unlikely to predominate the dinitrogen reduction mechanism when 1 is treated with KC8 under N-2.