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 N-2 or NO2 dissociation from the corresponding precursor species [(CF3)(3)Au(N-3)](-) 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.

Automated summary

This study discovered chemical species with Au-N and Au-O units and trapped them within a suitable organometallic frame. These compounds were experimentally detected and showed the characteristics of high-energy ions, making them of significant research value.