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 [(CF₃ )₃ AuN]^- and [(CF₃ )₃ AuO]^- 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 )₃ Au(N₃ )]^- and [(CF₃ )₃ Au(ONO₂ )]^- in the gas phase. Together with the known fluoride derivative [(CF₃ )₃ AuF]^- , they form an interesting series of isoleptic and alloelectronic complexes of the highly acidic organogold(iii) moiety (CF₃ )₃ Au with singly charged anions X^- of the most electronegative elements (X=F, O, N). Ligand-field inversion in all these [(CF₃ )₃ AuX]^- species results in the localization of unpaired electrons at the N and O atoms.