Extremely Efficient Catalysis of Carbon-Carbon Bond Formation Using Click Dendrimer-Stabilized Palladium Nanoparticles.docVIP

Molecules 2010, 15, 4947-4960; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Review Extremely Efficient Catalysis of Carbon-Carbon Bond Formation Using “Click” Dendrimer-Stabilized Palladium Nanoparticles Didier Astruc *, Cátia Ornelas, Abdou K. Diallo and Jaime Ruiz ISM, UMR CNRS N°5255, Université Bordeaux 1, 3305 Talence Cedex, France * Author to whom correspondence should be addressed; E-Mail: d.astruc@ism.u-bordeaux1.fr. Received: 24 June 2010; in revised form: 8 July 2010 / Accepted: 12 July 2010 / Published: 20 July 2010 Abstract: This article is an account of the work carried out in the authors’ laboratory illustrating the usefulness of dendrimer design for nanoparticle palladium catalysis. The “click” synthesis of dendrimers constructed generation by generation by 1?3 C connectivity, introduces 1,2,3-triazolyl ligands insides the dendrimers at each generation. Complexation of the ligands by PdII followed by reduction to Pd0 forms dendrimer- stabilized Pd nanoparticles (PdNPs) that are extremely reactive in the catalysis of olefin hydrogenation and C-C bond coupling reactions. The stabilization can be outer-dendritic for the small zeroth-generation dendrimer or intra-dendritic for the larger first- and second- generation dendrimers. The example of the Miyaura-Suzuki reaction that can be catalyzed by down to 1 ppm of PdNPs with a “homeopathic” mechanism (the less, the better) is illustrated here, including catalysis in aqueous solvents. Keywords: palladium; catalysis; nanoparticle; dendrimer; “click reaction” 1. Introduction Catalysis by dendrimers appeared 20 years ago when Shell patented van Leeuwen’s work on the catalysis of CO/alkene polymerization. This study involved the comparison between mononuclear and star-shaped hexaphosphine-palladium catalysts. The star-shaped catalyst gave 3% fouling whereas the mono-palladium catalyst