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This Account reports the synthesis and characterization of dendrimer-encapsulated metal nanoparticles and their applications to catalysis. These materials are prepared by sequestering metal ions within dendrimers followed by chemical reduction to yield the corresponding zerovalent metal nanoparticle. The size of such particles depends on the number of metal ions initially loaded into the dendrimer. Intradendrimer hydrogenation and carbon−carbon coupling reactions in water, organic solvents, biphasic fluorous/organic solvents, and supercritical CO2 are also described.

Ligand exchange reaction is a very important and useful tool for preparing functionalised metal nanoparticles. Understanding the mechanism of this process is essential for rational design of nanoparticle-based devices. However the underlying chemistry was found to be very rich. In this article, we summarise the research efforts of several groups to unravel the mechanisms of ligand exchange reaction, and discuss implications for future developments.