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Terminal Au−N and Au−O Units in Organometallic Frames
Author(s) -
PérezBitrián Alberto,
Alvarez Santiago,
Baya Miguel,
Echeverría Jorge,
Martín Antonio,
Orduna Jesús,
Menjón Babil
Publication year - 2023
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202203181
Subject(s) - chemistry , moiety , ion , dissociation (chemistry) , group 2 organometallic chemistry , crystallography , stereochemistry , molecule , organic chemistry
Abstract 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.