An Organogold(III) Difluoride with a trans Arrangement

The trans isomer of the organogold(III) difluoride complex [PPh4][(CF3)2AuF2] has been obtained in a stereoselective way and in excellent yield by reaction of [PPh4][CF3AuCF3] with XeF2 under mild conditions. The compound is both thermally stable and reactive. Thus, the fluoride ligands are stereosp...

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Bibliographic Details
Published in:Angewandte Chemie 2018-05, Vol.130 (22), p.6627-6631
Main Authors: Pérez‐Bitrián, Alberto, Baya, Miguel, Casas, José M., Martín, Antonio, Menjón, Babil, Orduna, Jesús
Format: Article
Language:English
Subjects:
Chemistry
Crystallography
Cyanides
Fluoride
Fluorides
Geometrische Isomerie
Gold
Identification methods
Stereochemistry
Stereoselektivität
Thermal stability
Trifluormethyl-Ligand
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Summary:The trans isomer of the organogold(III) difluoride complex [PPh4][(CF3)2AuF2] has been obtained in a stereoselective way and in excellent yield by reaction of [PPh4][CF3AuCF3] 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)2Au(CN)2]. The organogold fluoride complexes [CF3AuFx]− (x=1, 2, 3) have been experimentally detected to arise upon collision‐induced dissociation of the [trans‐(CF3)2AuF2]− anion in the gas phase. Their structures have been calculated by DFT methods. In the isomeric forms identified for the open‐shell species [CF3AuF2]−, 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 Auiii and Agiii have similar covalent radii, at least in their most common square‐planar geometry. In Form! Das trans‐Isomer des [(CF3)2AuF2]−‐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 [CF3AuFx]− (x=1, 2, 3).
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201802379