English   español  
Por favor, use este identificador para citar o enlazar a este item: http://hdl.handle.net/10261/111211
COMPARTIR / IMPACTO:
Estadísticas
logo share SHARE logo core CORE   Add this article to your Mendeley library MendeleyBASE

Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL
Exportar a otros formatos:
Título

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
Aurophilicity
Gold
Fecha de publicación2013
EditorWiley-VCH
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.
URIhttp://hdl.handle.net/10261/111211
DOI10.1002/chem.201302142
Identificadoresdoi: 10.1002/chem.201302142
issn: 0947-6539
e-issn: 1521-3765
Aparece en las colecciones: (ISQCH) Artículos
(ICMA) Artículos
Ficheros en este ítem:
Fichero Descripción Tamaño Formato  
accesoRestringido.pdf15,38 kBAdobe PDFVista previa
Visualizar/Abrir
Mostrar el registro completo
 

Artículos relacionados:


NOTA: Los ítems de Digital.CSIC están protegidos por copyright, con todos los derechos reservados, a menos que se indique lo contrario.