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Gold(I) and Gold(III) trifluoromethyl derivatives

AutorMartínez-Salvador, Sonia ; Falvello, Larry R.; Martín, Antonio ; Menjón, Babil
Palabras claveFluorinated compounds
C-F activation
Metal carbonyl derivatives
Organogold compounds
Fecha de publicación2013
CitaciónChemistry - A European Journal 19(43): 14540-14552 (2013)
ResumenTrifluoromethylation of AuCl3 by using the Me 3SiCF3/CsF system in THF and in the presence of [PPh 4]Br proceeds with partial reduction, yielding a mixture of [PPh 4][AuI(CF3)2] (1′) and [PPh4][AuIII(CF3)4] (2′) that can be adequately separated. An efficient method for the high-yield synthesis of 1′ is also described. The molecular geometries of the homoleptic anions [AuI(CF3)2]- and [Au III(CF3)4]- in their salts 1′ and [NBu4][AuIII(CF3)4] (2) have been established by X-ray diffraction methods. Compound 1′ oxidatively adds halogens, X2, furnishing [PPh4][Au III(CF3)2X2] (X=Cl (3), Br (4), I (5)), which are assigned a trans stereochemistry. Attempts to activate C-F bonds in the gold(III) derivative 2′ by reaction with Lewis acids under different conditions either failed or only gave complex mixtures. On the other hand, treatment of the gold(I) derivative 1′ with BF3× OEt2 under mild conditions cleanly afforded the carbonyl derivative [AuI(CF3)(CO)] (6), which can be isolated as an extremely moisture-sensitive light yellow crystalline solid. In the solid state, each linear F3C-Au-CO molecule weakly interacts with three symmetry-related neighbors yielding an extended 3D network of aurophilic interactions (Au⋯Au=345.9(1)pm). The high \tilde \nu CO value (2194cm-1 in the solid state and 2180cm-1 in CH 2Cl2 solution) denotes that CO is acting as a mainly σ-donor ligand and confirms the role of the CF3 group as an electron-withdrawing ligand in organometallic chemistry. Compound 6 can be considered as a convenient synthon of the >AuI(CF 3)> fragment, as it reacts with a number of neutral ligands L, giving rise to the corresponding [AuI(CF3)(L)] compounds (L=CNtBu (7), NCMe (8), py (9), tht (10)). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Identificadoresdoi: 10.1002/chem.201302142
issn: 0947-6539
e-issn: 1521-3765
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