An Organogold(III) Difluoride with a trans Arrangement. Issue 22 (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 international edition. Volume 57:Issue 22(2018)
• Page Start: 6517
• Page End: 6521
• Publication Date: 2018-04-26
• Subjects: fluorides -- geometric isomerism -- gold -- stereoselectivity -- trifluoromethyl ligand; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201802379
• Languages: English
• ISSNs: 1433-7851

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 shape ! The trans isomer of the [(CF3 )2 AuF2 ] − anion has been stereoselectively obtained and isolated in excellent yield. It furnishes the whole series of organogold fluoride complexes [CF3 AuF x ] − ( x =1, 2, 3) by collision‐induced dissociation in the gas phase.