Treatment of [FeIV(O)(TPA)(NCMe)](CF3SO 3)2 [TPA, N,N,N-tris(2-pyridylmethyl)amine] with 3 equiv of NR4X (X = CF3CO2, Cl, or Br) in MeCN at -40°C affords a series of metastable [FeIV(O)(TPA)(X)] + complexes. Some characteristic features of the S = 1 oxoiron(IV) unit are quite insensitive to the ligand substitution in the equatorial plane, namely, the Fe-O distances (1.65-1.66 Å), the energy (∼7114.5 eV) and intensity [25(2) units] of the 1s-to-3d transition in the X-ray absorption spectra, and the Mössbauer isomer shifts (0.01-0.06 mm·s -1) and quadrupole splittings (0.92-0.95 mm·s-1). The coordination of the anionic X ligand, however, is evidenced by red shifts of the characteristic near-IR ligand-field bands (720-800 nm) and spectroscopic observation of the bound anion by 19F NMR for X = CF 3CO2 and by EXAFS analysis for X = Cl (rFe-cl = 2.29 Å) and Br (rFe-Br = 2.43 Å). Density functional theory calculations yield Mössbauer parameters and bond lengths in good agreement with the experimental data and produce excited-state energies that follow the trend observed in the ligand-field bands. Despite mitigating the high effective charge of the iron(IV) center, the substitution of the MeCN ligand with monoanionic ligands X- decreases the thermal stability of [FeIV(O)(TPA)]2+ complexes. These anion-substituted complexes model the cis-X-FeIV=O units proposed in the mechanisms of oxygen-activating nonheme iron enzymes.