The CF₃ Group as a Synthon of the CF⁺ Unit in Palladium Chemistry

Joven-Sancho, Daniel ; Baya, Miguel (Universidad de Zaragoza) ; Martín, Antonio ; Orduna, Jesús ; Menjón, Babil

Resumen: 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.

Idioma: Inglés

DOI: 10.1002/anie.202403108

Año: 2024

Publicado en: Angewandte Chemie (International ed.) (2024), e202403108 [7 pp.]
ISSN: 1433-7851

Factor impacto JCR: 16.9 (2024)

Categ. JCR: CHEMISTRY, MULTIDISCIPLINARY rank: 15 / 239 = 0.063 (2024) - Q1 - T1

Factor impacto SCIMAGO: 5.55 - Chemistry (miscellaneous) (Q1) - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E17-23R
Financiación: info:eu-repo/grantAgreement/ES/DGA/E47-23R
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2021-122869NB-I00
Financiación: info:eu-repo/grantAgreement/ES/MINECO/BES-2016-078732

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)