112152 20230519145452.0 doi 10.1002/anie.202112449 sideral 126006 ART-2021-126006 eng Joven-Sancho, Daniel (orcid)0000-0002-0204-7713 A five-coordinate compound with inverted ligand field: an unprecedented geometry for silver(iii) 2021 Access copy available to the general public Unrestricted 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. info:eu-repo/grantAgreement/ES/DGA/E17-20R info:eu-repo/grantAgreement/ES/MICIU-FEDER/PGC2018-094749-B-I00 info:eu-repo/grantAgreement/ES/MINECO/BES-2016-078732 info:eu-repo/semantics/openAccess by-nc-nd http://creativecommons.org/licenses/by-nc-nd/3.0/es/ 16.823 2021 CHEMISTRY, MULTIDISCIPLINARY 15 / 180 = 0.083 2021 Q1 T1 5.126 2021 Chemistry (miscellaneous) 2021 Q1 Catalysis 2021 Q1 23.9 2021 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Baya, Miguel Universidad de Zaragoza (orcid)0000-0002-2492-625X Martin, Antonio (orcid)0000-0002-4808-574X Orduna, Jesús (orcid)0000-0003-3514-2570 Menjon, Babil (orcid)0000-0001-9045-5102 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 60, 51 (2021), 26545-26549 Angew. Chem. (Int. ed.) ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 1433-7851 954563 http://zaguan.unizar.es/record/112152/files/texto_completo.pdf Versión publicada 2939146 http://zaguan.unizar.es/record/112152/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:112152 articulos driver 2023-05-18-14:47:03 ARTICLE