doi:10.1002/chem.202303937engPueyo, J.Joven-Sancho, D.Martín, A.Menjón, B.Baya, M.The fluoride method: access to silver(III) NHC complexesART-2024-137672We have synthesized the first silver(III) carbene complexes, (CF3)3Ag(NHC), by direct reaction of the silver(III) fluoride precursor complex [PPh4][(CF3)3AgF] with different imidazolium salts. This novel methodology circumvents the use of free NHC molecules. The silver(III) carbene complexes thus prepared are unprecedented and show remarkable thermal stabilities. They display square-planar or square-pyramidal geometry. Following our calculations, the electronic structure of a model representative complex exhibits Inverse Ligand Field (ILF). The compounds reported herein are synthetic analogues of the elusive difluorocarbene and carbonyl species proposed as intermediates in the acidic decomposition of [Ag(CF3)4]−. The synthetic procedure reported is envisaged to enable access to carbene complexes of other late transition-metals in high oxidation states.2024http://zaguan.unizar.es/record/13279310.1002/chem.202303937http://zaguan.unizar.es/record/132793oai:zaguan.unizar.es:132793info:eu-repo/grantAgreement/ES/DGA/E17-23Rinfo:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00info:eu-repo/grantAgreement/ES/MINECO/BES-2016-078732Chemistry - A European Journal 30, 12 (2024), e202303937 [5 pp.]by-nc-ndhttps://creativecommons.org/licenses/by-nc-nd/4.0/deed.esinfo:eu-repo/semantics/openAccess