Interest in catalysis by metal nanoparticles (NPs) is increasing dramatically, as reflected by the large number of publications in the last five years. This field, "semi-heterogeneous catalysis", is at the frontier between homogeneous and heterogeneous catalysis, and progress has been made in the efficiency and selectivity of reactions and recovery and recyclability of the catalytic materials. Usually NP catalysts are prepared from a metal salt, a reducing agent, and a stabilizer and are supported on an oxide, charcoal, or a zeolite. Besides the polymers and oxides that used to be employed as standard, innovative stabilizers, media, and supports have appeared, such as dendrimers, specific ligands, ionic liquids, surfactants, membranes, carbon nanotubes, and a variety of oxides. Ligand-free procedures have provided remarkable results with extremely low metal loading. The Review presents the recent developments and the use of NP catalysis in organic synthesis, for example, in hydrogenation and C--C coupling reactions, and the heterogeneous oxidation of CO on gold NPs.

Nanoparticles as Recyclable Catalysts: The Frontier between Homogeneous and Heterogeneous Catalysis

2.5. Stabilization of IL Emulsions by Nanoparticles 2623 3. Hydrogenations in ILs 2623 3.1. Hydrogenation on IL-Stabilized Nanoparticles 2623 3.1.1. Hydrogenation of 1,3-Butadiene 2623 3.1.2. Hydrogenation of Alkenes and Arenes 2624 3.1.3. Hydrogenation of Ketones 2624 3.2. Homogeneous Catalytic Hydrogenation in ILs 2624 3.3. Hydrogenation of Functionalized ILs 2625 3.3.1. Selective Hydrogenation of Polymers 2625 3.4. Asymmetric Hydrogenations 2626 3.4.1. Enantioselective Hydrogenation 2626 3.5. Role of the ILs Purity in Hydrogenation Reactions 2628

Catalysis in ionic liquids

A wide array of forms of palladium has been utilized as precatalysts for Heck and Suzuki coupling reactions over the last 15 years. Historically, nearly every form of palladium used has been described as the active catalytic species. However, recent research has begun to shed light on the in situ transformations that many palladium precatalysts undergo during and before the catalytic reaction, and there are now many suggestions in the literature that narrow the scope of types of palladium that may be considered true “catalysts” in these coupling reactions. In this work, for each type of precatalyst, the recent literature is summarized and the type(s) of palladium that are proposed to be truly active are enumerated. All forms of palladium, including discrete soluble palladium complexes, solid-supported metal ligand complexes, supported palladium nano- and macroparticles, soluble palladium nanoparticles, soluble ligand-free palladium, and palladium-exchanged oxides are considered and reviewed here. A considerable focus is placed on solid precatalysts and on evidence for and against catalysis by solid surfaces vs. soluble species when starting with various precatalysts. The review closes with a critical overview of various control experiments or tests that have been used by authors to assess the homogeneity or heterogeneity of catalyst systems.

On the Nature of the Active Species in Palladium Catalyzed Mizoroki–Heck and Suzuki–Miyaura Couplings – Homogeneous or Heterogeneous Catalysis, A Critical Review

Ionic liquids in catalysis

Recovery and reuse of expensive catalysts after catalytic reactions are important factors for sustainable process management. The aim of this Review is to highlight the progress in the formation and catalytic applications of magnetic nanoparticles and magnetic nanocomposites. Directed functionalization of the surfaces of nanosized magnetic materials is an elegant way to bridge the gap between heterogeneous and homogeneous catalysis. The introduction of magnetic nanoparticles in a variety of solid matrices allows the combination of well-known procedures for catalyst heterogenization with techniques for magnetic separation.

Magnetically Separable Nanocatalysts: Bridges between Homogeneous and Heterogeneous Catalysis

Ultrasound promoted C–C bond formation: Heck reaction at ambient conditions in room temperature ionic liquids

Ultrasound promoted Suzuki cross-coupling reactions in ionic liquid at ambient conditions.

A regioselective one-pot synthesis of 2-aryl benzimidazoles, benzoxazoles and benzthiazoles has been achieved in excellent isolated yields under ambient conditions using the ionic liquids, 1-butylimidazolium tetraflouroborate ([Hbim]BF4) and 1,3-di-n-butylimidazolium tetrafluoroborate ([bbim]BF4) as reaction media and promoters. There was no need for the use of an additional catalyst normally employed in the methodologies reported so far.

K. V. Srinivasan

Papers

Ultrasound promoted C–C bond formation: Heck reaction at ambient conditions in room temperature ionic liquids

Ultrasound promoted Suzuki cross-coupling reactions in ionic liquid at ambient conditions.

Room temperature ionic liquid promoted regioselective synthesis of 2-aryl benzimidazoles, benzoxazoles and benzthiazoles under ambient conditions

Ionic liquid promoted novel and efficient one pot synthesis of 3,4-dihydropyrimidin-2-(1H)-ones at ambient temperature under ultrasound irradiation

Ultrasound promoted acetylation of alcohols in room temperature ionic liquid under ambient conditions