Long-term stable 3 nm gold nanoparticles are prepared by a simple reaction between HAuCl4 and sodium borohydride in water under ambient conditions which very efficiently catalyze 4-nitrophenol reduction to 4-nitroaniline.

Catalysis by palladium derivatives is now one of the most important tools in organic synthesis. Whether researchers design palladium nanoparticles (NPs) or nanoparticles occur as palladium complexes decompose, these structures can serve as central precatalysts in common carbon-carbon bond formation. Palladium NPs are also valuable alternatives to molecular catalysts because they do not require costly and toxic ligands. In this Account, we review the role of "homeopathic" palladium catalysts in carbon-carbon coupling reactions. Seminal studies from the groups of Beletskaya, Reetz, and de Vries showed that palladium NPs can catalyze Heck and Suzuki-Miyaura reactions with aryl iodides and, in some cases, aryl bromides at part per million levels. As a result, researchers coined the term "homeopathic" palladium catalysis. Industry has developed large-scale applications of these transformations. In addition, chemists have used Crooks' concept of dendrimer encapsulation to set up efficient nanofilters for Suzuki-Miyaura and selective Heck catalysis, although these transformations required high PdNP loading. With arene-centered, ferrocenyl-terminated dendrimers containing triazolyl ligands in the tethers, we designed several generations of dendrimers to compare their catalytic efficiencies, varied the numbers of Pd atoms in the PdNPs, and examined encapsulation vs stabilization. The catalytic efficiencies achieved "homeopathic" (TON = 540 000) behavior no matter the PdNP size and stabilization type. The TON increased with decreasing the Pd/substrate ratio, which suggested a leaching mechanism. Recently, we showed that water-soluble arene-centered dendrimers with tri(ethylene glycol) (TEG) tethers stabilized PdNPs involving supramolecular dendritic assemblies because of the interpenetration of the TEG branches. Such PdNPs are stable and retain their "homeopathic" catalytic activities for Suzuki-Miyaura reactions for months. (TONs can reach 2.7 × 10(6) at 80 °C for aryl bromides and similar values for aryl iodides at 28 °C.) Sonogashira reactions catalyzed by these PdNPs are quantitative with only 0.01% Pd/mol substrate. Kato's group has reported remarkable catalytic efficiencies for mesoporous catalysts formed by polyamidoamine (PAMAM) dendrimer polymerizations. These and other mesoporous structures could allow for catalyst recycling, with efficiencies approaching the "homeopathic" behavior. In recent examples of Suzuki-Miyaura reactions of aryl chlorides, chemists achieved truly "homeopathic" catalysis when a surfactant such as a tetra-n-butylammonium halide or an imidazolium salt was used in stoichiometric quantities with substrate. These results suggest that the reactive halide anion of the salt attacks the neutral Pd species to form a palladate. In the case of aryl chlorides, the reaction may occur through the difficult, rate-limiting oxidative-addition step.

Upon catalyst and substrate encapsulation, an amphiphilic dendrimer containing 27 triethylene glycol termini and 9 intradendritic triazole rings serves as a catalytic nanoreactor by considerably accelerating the Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) "click" reactions of various substrates in water using the catalyst Cu(hexabenzyltren)Br (tren = triaminoethylamine). Moreover this recyclable nanoreactor with intradendritic triazole rings strongly also activates the simple Sharpless-Fokin catalyst CuSO4 + sodium ascorbate in water under ambient conditions leading to exceptional TONs up to 510,000. This fully recyclable catalytic nanoreactor allows to considerably decrease the amount of this cheap copper catalyst down to industrially tolerable residues, and some biomedical and cosmetic applications are exemplified.

The stereoelectronic properties of the stabilizing ligands of gold nanoparticles (AuNPs) are shown to play a considerable role in their catalytic efficiency for 4-nitrophenol reduction by NaBH4, consistent with a mechanism involving restructuration of the AuNP surface that behaves as an "electron reservoir".

Nanoparticles (Pd, Pt, Rh) stabilized by G4OH PAMAM dendrimers and supported in SBA-15 (MNPs/SBA-15 with M = Pd, Pt, Rh) were efficiently used as catalysts in the acceptorless dehydrogenation of tetrahydroquinoline/indoline derivatives in toluene (release of H) at 130 °C. These catalysts are air stable, very active, robust, and recyclable during the process. The reverse hydrogenation reaction of quinoline derivatives (H storage) was also optimized and successfully performed in the presence of the same catalysts in toluene at 60 °C under only 1 atm of hydrogen gas. Such catalysts may be essential for the adoption of organic hydrogen-storage materials as an alternative to petroleum-derived fuels. Hot filtration test confirmed that the reaction follows a heterogeneous pathway. Moreover, PdNPs/SBA-15 was an excellent catalyst for the direct arylation at the C-2 position (via C-H activation) of indole in water in the presense of a hypervalent iodine oxidant. Thus, a one-pot dehydrogenation/direct arylation cascade reaction between indoline and an arylated agent was efficaciously performed in water, demonstrating the potential of the system to catalyze tandem heterogeneous/homogeneous processes by choice of the appropriate oxidant/reductant.

Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles-some without homogeneous analogues-for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimize and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence, and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g., π-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g., oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl) or reduced (e.g., with H) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous cata...

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Metathesis reactions are now essential for the synthesis of complex organic molecules; a large variety of useful materials are available, and progress in this field is growing rapidly. Emphasis in this review on metathesis is placed on the recent developments of stereoselectivity aspects by using new families of molybdenum (Schrock type) and ruthenium (Grubbs type) catalysts for olefin metathesis. Recent progress in alkyne metathesis catalysts (Fürstner type) and their properties and impressive synthetic applications are highlighted as well as new terminal alkyne metathesis catalysts (Tamm type). The various strategies involved in recovering the catalyst and removing metal impurities from products towards “green chemistry” are briefly reviewed. The relationship of olefin metathesis is shown with the alkyne metathesis reaction that was exploited by Fürstner, with alkane metathesis that was achieved by using surface organometallic chemistry and highlighted by Basset, and with the use of classic organometallic catalysts by the Goldman and Brookhart groups. Finally, recent developments in polymer chemistry that involve stereochemical control, low polydispersities, and applications are summarized.