Resumen: 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. Idioma: Inglés DOI: 10.1002/chem.202203181 Año: 2023 Publicado en: Chemistry - A European Journal 29, 8 (2023), e202203181 [7 pp.] ISSN: 0947-6539 Factor impacto JCR: 3.9 (2023) Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 80 / 231 = 0.346 (2023) - Q2 - T2 Factor impacto CITESCORE: 7.9 - Organic Chemistry (Q1) - Catalysis (Q2)