Synthesis and characterization of dodecylamine-capped ultrasmall metallic palladium nanoparticles (2 nm)

Dodecylamine-coated ultrasmall palladium nanoparticles were prepared by reduction of dichlorido(1,5-cyclooctadiene)palladium(ii) with tert-butylamine borane in benzene. The synthesis yielded several tens of milligrams per batch. The nature of the metal core as well as the ligand shell was elucidated by a combination of complementary methods. The particles had a diameter of about 2 nm (metallic core; by small-angle X-ray scattering and transmission electron microscopy) and a hydrodynamic diameter of about 5.4 nm (by ¹H-NMR DOSY in benzene). They were easily dispersible in organic solvents. The ligand shell was thoroughly investigated by ¹H and ¹³C NMR spectroscopy in dispersion, revealing about 170 ligand molecules on the surface of each 2 nm particle. X-ray powder diffraction (Rietveld refinement) and total-scattering pair distribution function analysis (PDF) showed metallic palladium nanoparticles with a crystallite size of about 2 nm, indicating a mostly single-domain nature of the nanoparticle core. X-ray photoelectron spectroscopy confirmed metallic nanoparticles also but detected oxidized palladium species.