The reactivity of the trigonal bipyramidal iron(I) complex [SiP3iPr]Fe(N-2) ([SiP3iPr] = (2-iPr(2)PC(6)H(4))(3)Si-) toward organoazides has been examined. 1-Adamantylazide was found to coordinate the iron center to form stable [SiP3iPr]Fe(eta(1)-N(3)Ad). Aryl azides instead afforded unstable [SiP3iPr]Fe(N3Ar) species that decayed gradually to regenerate [SiP3iPr]Fe(N-2) with release of azoarenes (ArN=NAr). The conversion of aryl azides to azoarenes can thus be achieved catalytically. Competitive trapping experiments strongly suggest the intermediacy of reactive nitrene complexes of the type [SiP3iPr]Fe(NAr) that couple bimolecularly in the N-N bond forming step. Evidence for one such intermediate was provided by electron paramagnetic resonance spectroscopy via photolysis of [SiP3iPr]Fe(N3Ar) in a frozen glass. The electronic structures of these putative nitrene intermediates have been examined by DFT methods.