A five-coordinate compound with inverted ligand field: an unprecedented geometry for silver(iii)

Joven-Sancho, Daniel ; Baya, Miguel (Universidad de Zaragoza) ; Martin, Antonio ; Orduna, Jesús ; Menjon, Babil

Resumen: By using suitable synthetic procedures, we have first isolated the square-planar organosilver(III) compounds [PPh4][trans-(CF3)(2)AgX2] [X=Cl (1 a), Br (2 a)]. The geometry and stereochemistry of the chloro-derivative 1 a have been unambiguously established by single-crystal X-ray diffraction (SC-XRD) methods. Following our calculations on the relative stability of the cis-/trans-[(CF3)(2)AgX2](-) couples (X=F, Cl, Br, I), the experimentally obtained compounds 1 a and 2 a appear to be kinetically favored stereoisomers. They display some tendency to associate an additional X- ligand affording rare five-coordinate Ag-III species [(CF3)(2)AgX3](2-). Interestingly, compound [PPh4](2)[(CF3)(2)AgBr3] (3) has been identified by SC-XRD methods as the first Ag-III derivative with trigonal symmetry in general and trigonal bipyramidal geometry in particular. This unusual five-coordinate species also exhibits inverted ligand field.

Idioma: Inglés

DOI: 10.1002/anie.202112449

Año: 2021

Publicado en: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60, 51 (2021), 26545-26549
ISSN: 1433-7851

Factor impacto JCR: 16.823 (2021)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 15 / 180 = 0.083 (2021) - Q1 - T1

Factor impacto CITESCORE: 23.9 - Chemical Engineering (Q1)

Factor impacto SCIMAGO: 5.126 - Chemistry (miscellaneous) (Q1) - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E17-20R
Financiación: info:eu-repo/grantAgreement/ES/MICIU-FEDER/PGC2018-094749-B-I00
Financiación: info:eu-repo/grantAgreement/ES/MINECO/BES-2016-078732

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)