Alkyne-Functionalized Ruthenium Nanoparticles: Ruthenium- Vinylidene Bonds at the Metal-Ligand Interface

摘要

Stable ruthenium nanoparticles were prepared by the self-assembly of 1-dodecyne onto the "bare" Ru colloid surface. The formation of a Ru-vinylidene (Ru=C=CH-R) interfacial bonding linkage was confirmed by the specific reactivity of the nanoparticles with imine derivatives to form a heterocyclic complex at the metal-ligand interface, as manifested in ~1H and ~(13)C NMR, photoluminescence, and electrochemical measurements in which a ferrocenyl imine was used as the labeling probe. Notably, the resulting nanoparticles could also undergo olefin metathesis reactions with vinyl-terminated molecules, as exemplified by the functionalization of the nanoparticles with 1-vinylpyrene. In sharp contrast, no reactvity was observed with 1-dodecynide-stabilized ruthenium nanoparticles with either imine or vinyl derivatives, indicating that these (deprotonated) nanoparticles were stabilized instead by the formation of a Ru-C≡dπ bond at the metal-ligand interface.