Grignard Functionalization of Weinreb Amide-Modified Au Nanoparticles

Reactions of Grignard and organolithium reagents are staple transformations in organic chemistry. However, their use in the chemical functionalization of monolayer-protected metallic nanoparticles is unprecedented. In this letter, we report the reaction of Au nanoparticles bearing a mixed monolayer of alkanethiol ligands that are methyl- and N-methoxy-N-methyl amide-terminated. The latter of these rapidly undergoes reaction with organometallic reagents, achieving high yields (in some cases, nearly quantitative) in only a few hours without the need for high pressure, temperature or catalysts. We assess the feasibility of this reaction with a range of organometallic reagents on the basis of both surface reaction yield and also the stability of the particles (defined as the mass % Au particles recovered vs a control). Demonstrating the utility of these strong organometallic reagents opens the door to a large class of reactions that are underutilized within the field of nanomaterials.