The chemical oxidation and subsequent group transfer activity of the unusual diiron imido complexes Fe((PrNPPh2)-Pr-i)(3)Fe equivalent to NR (R = tert-butyl (Bu-t), 1; adamantyl, 2) was examined. Bulk chemical oxidation of 1 and 2 with Fc[PF6] (Fc = ferrocene) is accompanied by fluoride ion abstraction from PF6- by the iron center trans to the Fe equivalent to NR functionality, forming F-Fe((PrNPPh2)-Pr-i)(3)Fe equivalent to NR (Pr-i = isopropyl) (R = Bu-t, 3; adamantyl, 4). Axial halide ligation in 3 and 4 significantly disrupts the Fe-Fe interaction in these complexes, as is evident by the >0.3 angstrom increase in the intermetallic distance in 3 and 4 compared to 1 and 2. Mossbauer spectroscopy suggests that each of the two pseudotetrahedral iron centers in 3 and 4 is best described as Fe-III and that one-electron oxidation has occurred at the tris(amido)-ligated iron center. The absence of electron delocalization across the Fe-Fe equivalent to NR chain in 3 and 4 allows these complexes to readily react with CO and (BuNC)-Bu-t to generate the (FeFeI)-Fe-III complexes F-Fe((PrNPPh2)-Pr-i)(3)Fe(CO)(2) (5) and F-Fe((PrNPPh2)-Pr-i)(3)Fe((BuNC)-Bu-t)(2) (6), respectively. Computational methods are utilized to better understand the electronic structure and reactivity of oxidized complexes 3 and 4.