The reaction of Fe(N{SiMe3}(2))(2) (1) with 1 equiv of arylthiol (ArSH) results in material of notional composition Fe(SAr)(N{SiMe3}(2)) (2), from which crystalline Fe-2(mu-SAr)(2)(N{SiMe3}(2))(2)(THF)(2) (Ar = Mes) can be isolated from tetrahydrofuran (THF) solvent. Treatment of 2 with 0.5 equiv of 1,2-diarylhydrazine (Ar'NH-NHAr', Ar' = Ph, p-Tol) yields ferric-imide-thiolate cubanes Fe-4(mu(3)-NAr')(4)(SAr)(4) (3). The site-differentiated, 1-electron reduced iron-imide cubane derivative [Fe(THF)(6)][Fe-4(mu(3)-N-P-Tol)(4)(SDMP)(3)(N{SiMe3}(2))](2) ([Fe(THF)(6)][4](2); DMP = 2,6-dimethylphenyl) can be isolated by adjusting the reaction stoichiometry of 1/ArSH/Ar'NHNHAr' to 9:6:5. The isolated compounds were characterized by a combination of structural (X-ray diffraction), spectroscopic (NMR, UV-vis, Mossbauer, EPR), and magnetochemical methods. Reactions with a range of hydrazines reveal complex chemical behavior that includes not only N-N bond reduction for 1,2-di- and trisubstituted arylhydrazines, but also catalytic disproportionation for 1,2-diarylhydrazines, N-C bond cleavage for 1,2-diisopropylhydrazine, and no reaction for hindered and tetrasubstituted hydrazines.