Resumen: We 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. Idioma: Inglés DOI: 10.1002/chem.202303937 Año: 2024 Publicado en: Chemistry - A European Journal 30, 12 (2024), e202303937 [5 pp.] ISSN: 0947-6539 Factor impacto JCR: 3.7 (2024) Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 95 / 239 = 0.397 (2024) - Q2 - T2 Factor impacto SCIMAGO: 0.981 - Chemistry (miscellaneous) (Q1) - Organic Chemistry (Q1) - Catalysis (Q2)