Since gold is located well beyond the oxo wall, chemical species with terminal Au-N and Au-O units are extremely rare and limited to low coordination numbers. We report here that these unusual units can be trapped within a suitable organometallic frame. Thus, the terminal auronitrene and auroxyl derivatives, [(CF₃)₃AuN]^- and [(CF₃)₃AuO]^- were identified as local minima by calculation. These open-shell, high-energy ions were experimentally detected by tandem mass spectrometry (MS²): They respectively arise by N₂ or NO₂ dissociation from the corresponding precursor species [(CF₃)₃Au(N₃)]^- and [(CF₃)₃Au(ONO₂)]^- in the gas phase. Together with the known fluoride derivative [(CF₃)₃AuF]^- , they form an interesting series of isoleptic and alloelectronic complexes of the highly acidic organogold(III) moiety (CF₃)₃Au with singly charged anions X^- of the most electronegative elements (X = F, O, N). Ligand-field inversion in all these [(CF₃)₃AuX]^- species results in the localization of unpaired electrons at the N and O atoms.