135325 20260217205535.0 doi 10.1002/anie.202403108 sideral 138584 ART-2024-138584 eng Joven-Sancho, Daniel (orcid)0000-0002-0204-7713 The CF₃ Group as a Synthon of the CF⁺ Unit in Palladium Chemistry 2024 Access copy available to the general public Unrestricted The homoleptic trifluoromethyl‐palladium(II) complex [Pd(CF3)4]2− (1) is shown to be highly active towards amines. Thus, when treated with primary amines RNH2, it readily undergoes aminolysis of one of the CF3 ligands affording the isocyanide complexes [(CF3)3Pd(CNR)]− (R=aryl). In this process the original CF3 group undergoes total defluorination. Interestingly, the reaction of 1 with secondary amines R2NH proceeds with loss of just two F‐substituents, whereby the Fischer‐type fluoroaminocarbene complexes [(CF3)3Pd(CFNR2)]− are formed (R=Et, Ph). The reaction of 1 with diamines affords different [(CF3)3Pd(NHC)]− complexes containing sterically non‐demanding NHC ligands. Representative examples of various topologies are reported based on the common imidazolidin‐2‐ylidene or benzimidazolin‐2‐ylidene rings as well as the expanded‐ring perimidin‐2‐ylidene. This metal‐tailored synthetic route, where a CF3 group acts as a pre‐carbenic unit, is unprecedented in the vast NHC‐chemistry. It takes place under very mild conditions and is envisaged to be extensible to other non‐isolable NHC ligands. The key difluorocarbene intermediate [(CF3)3Pd(CF2)]− is experimentally detected. info:eu-repo/grantAgreement/ES/DGA/E17-23R info:eu-repo/grantAgreement/ES/DGA/E47-23R info:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00 info:eu-repo/grantAgreement/ES/MINECO/BES-2016-078732 info:eu-repo/semantics/openAccess by-nc-nd https://creativecommons.org/licenses/by-nc-nd/4.0/deed.es 17.0 2024 CHEMISTRY, MULTIDISCIPLINARY 15 / 239 = 0.063 2024 Q1 T1 5.55 2024 Chemistry (miscellaneous) 2024 Q1 Catalysis 2024 Q1 27.6 2024 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Baya, Miguel Universidad de Zaragoza (orcid)0000-0002-2492-625X Martín, Antonio Orduna, Jesús (orcid)0000-0003-3514-2570 Menjón, Babil (orcid)0000-0001-9045-5102 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica (2024), e202403108 [7 pp.] Angew. Chem. (Int. ed.) Angewandte Chemie (International ed.) 1433-7851 1437041 http://zaguan.unizar.es/record/135325/files/texto_completo.pdf Versión publicada 2891806 http://zaguan.unizar.es/record/135325/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:135325 articulos driver 2026-02-17-20:33:58 ARTICLE