doi:10.1002/anie.202112449engJoven-Sancho, DanielBaya, MiguelMartin, AntonioOrduna, JesúsMenjon, BabilA five-coordinate compound with inverted ligand field: an unprecedented geometry for silver(iii)ART-2021-126006By 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.2021http://zaguan.unizar.es/record/11215210.1002/anie.202112449http://zaguan.unizar.es/record/112152oai:zaguan.unizar.es:112152info:eu-repo/grantAgreement/ES/DGA/E17-20Rinfo:eu-repo/grantAgreement/ES/MICIU-FEDER/PGC2018-094749-B-I00info:eu-repo/grantAgreement/ES/MINECO/BES-2016-078732ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60, 51 (2021), 26545-26549by-nc-ndhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccess