This work demonstrates the synthesis and properties of bis(trifluoromethyl)amido complexes in coinage metals, suggesting their potential applications.
A series of bis(trifluoromethyl)amido coinage metal(I) complexes were synthesized in yields of 52-93%. This includes N-heterocyclic carbene (NHC) complexes of copper(I), silver(I), and gold(I). In addition, the complex [(Ph₃P)Au{N(CF₃)₂}] was obtained in 70% yield. The complexes are thermally robust, with decomposition temperatures of 151-259 °C (DSC onset), and they were characterized by spectroscopic methods and elemental analysis. The bis(trifluoromethyl)amido complexes [(IDipp)M{N(CF₃)₂}] (M = Cu, Ag, Au), [(ItBu)M{N(CF₃)₂}] (M = Cu, Ag), and [(Ph₃P)Au{N(CF₃)₂}] were studied by single-crystal X-ray diffraction (SCXRD). A detailed analysis of selected bond parameters, aided by DFT calculations and ETS-NOCV studies, provided insight into the properties of the {N(CF₃)₂}⁻ ligand. The bis(trifluoromethyl)amido ligand is a weaker σ-donor than related nonfluorinated dialkylamido ligands, for example {N(CH₃)₂}⁻ and {NiPr₂}⁻. In addition, the salts [Ag(IDipp)₂]⁺([Ag{N(CF₃)₂}₂]⁻)0.25(Cl⁻)0.75, [Ag(ItBu)₂]⁺(HF₂)⁻, {[tBu₂Im]⁺}₂{N(CF₃)₂}⁻(HF₂)⁻, and [tBu₂Im]⁺(HF₂)⁻ were characterized by SCXRD.
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Schneider et al. (2026) studied this question.
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