Coinage metal metallacycles involving a fluorinated 3,5-diarylpyrazolate

摘要

Copper(I) and silver(I) pyrazolate complexes {[3,5-(3,5-(CF3)(2)Ph)(2)Pz]Cu}(3) and {[3,5-(3,5-(CF3)(2)Ph)(2)Pz]Ag}(3) have been synthesized using the fluorinated 3,5-(diaryl)pyrazole 3,5-(3,5-(CF3)(2)Ph)(2)PzH and copper(I) oxide and silver(I) oxide, respectively. The gold(I) analog was obtained from a reaction between Au(THT)Cl and [3,5-(3,5-(CF3)(2)Ph)(2)Pz]H/NaH. The X-ray crystal structures show that the coinage metal complexes {[3,5-(3,5-(CF3)(2)Ph)(2)Pz]M}(3) (M = Cu, Ag, Au) are trinuclear in the solid state. They feature distorted nine-membered M3N6 metallacyclic cores. The M-N distances follow Cu o Au o Ag, which is the trend expected from covalent radii of the corresponding coinage metal ions. The 3,5-(3,5-(CF3)(2)Ph)(2)PzH forms hydrogen bonded trimers in the solid state that are further organized by p-stacking between aryl rings. Solid samples of {[3,5-(3,5-(CF3)(2)Ph)(2)Pz]M}(3) display blue photoluminescence. The copper complex {[3,5-(3,5-(CF3)(2)Ph)(2)Pz]Cu}(3) is an excellent catalyst for mediating azide-alkyne cycloaddition chemistry.