Terminal Au−N and Au−O Units in Organometallic Frames

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 [(CF(3))(3)AuN](−) and [(CF(3))(3)AuO](−) were identified as local minima by calculation. These open‐shell, high‐energy ions were experimentally detected by tandem mass spectrometry (MS(2)): They respectively arise by N(2) or NO(2) dissociation from the corresponding precursor species [(CF(3))(3)Au(N(3))](−) and [(CF(3))(3)Au(ONO(2))](−) in the gas phase. Together with the known fluoride derivative [(CF(3))(3)AuF](−), they form an interesting series of isoleptic and alloelectronic complexes of the highly acidic organogold(iii) moiety (CF(3))(3)Au with singly charged anions X(−) of the most electronegative elements (X=F, O, N). Ligand‐field inversion in all these [(CF(3))(3)AuX](−) species results in the localization of unpaired electrons at the N and O atoms.