An Organogold(III) Difluoride with a trans Arrangement. (26th April 2018)

• Record Type: Journal Article
• Authors: Pérez‐Bitrián, Alberto; Baya, Miguel; Casas, José M.; Martín, Antonio; Menjón, Babil; Orduna, Jesús
• Is Part Of: Angewandte Chemie. Volume 130:Number 22(2018)
• Page Start: 6627
• Page End: 6631
• Publication Date: 2018-04-26
• Subjects: Fluoride -- Geometrische Isomerie -- Gold -- Stereoselektivität -- Trifluormethyl-Ligand; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201802379
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The trans isomer of the organogold(III) difluoride complex [PPh4 ][(CF3 )2 AuF2 ] has been obtained in a stereoselective way and in excellent yield by reaction of [PPh4 ][CF3 AuCF3 ] with XeF2 under mild conditions. The compound is both thermally stable and reactive. Thus, the fluoride ligands are stereospecifically replaced by any heavier halide or by cyanide, the cyanide affording [PPh4 ][ trans ‐(CF3 )2 Au(CN)2 ]. The organogold fluoride complexes [CF3 AuF x ] − ( x =1, 2, 3) have been experimentally detected to arise upon collision‐induced dissociation of the [ trans ‐(CF3 )2 AuF2 ] − anion in the gas phase. Their structures have been calculated by DFT methods. In the isomeric forms identified for the open‐shell species [CF3 AuF2 ] −, the spin density residing on the metal center is found to strongly depend on the precise stereochemistry. Based on crystallographic evidence, it is concluded that Au iii and Ag iii have similar covalent radii, at least in their most common square‐planar geometry. Abstract : In Form ! Das trans ‐Isomer des [(CF3 )2 AuF2 ] − ‐Anions wurde stereoselektiv erhalten und in Form eines Salzes in exzellenten Ausbeuten isoliert. Seine stoßinduzierte Dissoziation in der Gasphase liefert die vollständige Serie der Organogoldfluorid‐Komplexe [CF3 AuF x ] − ( x =1, 2, 3).