Gold nanoparticles stabilized by phosphine-decorated polymer immobilized ionic liquids (AuNP@PPh2-PIILP) is an extremely efficient multiproduct selective catalyst for the sodium borohydride-mediated reduction of nitrobenzene giving N-phenylhydroxylamine, azoxybenzene, or aniline as the sole product under mild conditions and a very low catalyst loading. The use of a single nanoparticle-based catalyst for the partial and complete reduction of nitroarenes to afford three different products with exceptionally high selectivities is unprecedented. Under optimum conditions, thermodynamically unfavorable N-phenylhydroxylamine can be obtained as the sole product in near quantitative yield in water, whereas a change in reaction solvent to ethanol results in a dramatic switch in selectivity to afford azoxybenzene. The key to obtaining such a high selectivity for N-phenylhydroxylamine is the use of a nitrogen atmosphere at room temperature as reactions conducted under an inert atmosphere occur via the direct pathway and are essentially irreversible, while reactions in air afford significant amounts of azoxy-based products by virtue of competing condensation due to reversible formation of N-phenylhydroxylamine. Ultimately, aniline can also be obtained quantitatively and selectively by adjusting the reaction temperature and time accordingly. Introduction of PEG onto the polyionic liquid resulted in a dramatic improvement in catalyst efficiency such that N-phenylhydroxylamine could be obtained with a turnover number (TON) of 100 000 (turnover frequency (TOF) of 73 000 h–1, with >99% selectivity), azoxybenzene with a TON of 55 000 (TOF of 37 000 h–1 with 100% selectivity), and aniline with a TON of 500 000 (TOF of 62 500 h–1, with 100% selectivity). As the combination of ionic liquid and phosphine is required to achieve high activity and selectivity, further studies are currently underway to explore whether interfacial electronic effects influence adsorption and thereby selectivity and whether channeling of the substrate by the electrostatic potential around the AuNPs is responsible for the high activity. This is the first report of a AuNP-based system that can selectively reduce nitroarenes to either of two synthetically important intermediates as well as aniline and, in this regard, is an exciting discovery that will form the basis to develop a continuous flow process enabling facile scale-up.

Palladium nanoparticles stabilized by heteroatom donor-modified polystyrene-based polymer immobilized ionic liquids (PdNP@HAD-PIILP; HAD-PPh 2 , OMe, NH 2 , CN, pyrrolidone) are highly efficient catalysts for the Suzuki-Miyaura cross-coupling in aqueous media under mild conditions. Catalyst modified with phosphine was consistently the most efficient as it gave high yields across a range of substrates under mild conditions at low catalyst loadings. Incorporation of polyethylene glycol into the phosphine modified immobilised ionic liquid support improved catalyst efficacy by improving dispersibility and facilitating access to the active site. Moreover, each of the heteroatom modified catalysts was more active than the corresponding unsubstituted imidazolium-based polystyrene benchmark as well as commercial samples of Pd/ C. Catalyst generated in situ from either [PdCl 4 ]@PPh 2 -PIILP or its PEGylated counterpart [PdCl 4 ]@PPh 2 -PEGPIILP, by reduction with phenylboronic acid, outperformed their pre-formed counterparts for the vast majority of substrates examined. The turnover frequency of 16,300 h À1 obtained at room temperature is one of the highest to be reported for palladium nanoparticle-catalysed Suzuki-Miyaura cross-coupling between 4bromoacetophenone and phenylboronic acid in aqueous media under such mild conditions.

Phosphino-decorated polymer immobilised ionic liquid-stabilised PdNPs are highly efficient catalysts for the aqueous phase hydrogenation and transfer hydrogenation of aromatic nitro compounds in batch and continuous flow.

An aqueous phase hydrogenation of α,β-unsaturated aldehydes with remarkable selectivity for the CC double bond under mild conditions.

Styrene-based peroxotungstate-modified polymer immobilized ionic liquid phase catalysts [PO4{WO(O2)2}4]@ImPIILP (Im = imidazolium) are remarkably efficient systems for the selective oxidation of sulfides under mild conditions both in batch and as a segmented or continuous flow process using either ethanol or acetonitrile as solvent or mobile phase, respectively. The performance of these styrene-based systems has been compared against their Ring Opening Metathesis Polymerisation derived counterparts to assess their relative merits. A comparative survey revealed catalyst supported on N-benzyl imidazolium decorated polymer immobilised ionic liquid to be the most efficient and a cartridge packed with a mixture of [PO4{WO(O2)2}4]@ImPIILP and silica operated as a segmented or continuous flow system giving good conversions and high selectivity for sulfoxide. The immobilised catalyst remained highly active for the sulfoxidation of thioanisole in ethanol with a stable conversion-selectivity profile for up to 8 h under continuous flow operation; for comparison conversions with a mixture of [NBu4]3[PO4{WO(O2)2}4] and silica dropped dramatically after only 15 min as a result of rapid leaching while [PO4{WO(O2)2}4]@ImPIILP prepared from commercially available Merrifield resin also gave consistently lower conversions; these benchmark comparisons serve to underpin the potential benefits of preparing the polymer immobilized ionic liquid supports.

Impregnation of phosphine-decorated styrene-based Polymer Immobilized Ionic Liquid (PPh2-PIIL) with ruthenium (III) trichloride resulted in facile reduction of the ruthenium to afford Ru(II) impregnated phosphine oxide-decorated PIIL (O=PPh2PIIL). The derived...

The need having arisen for a small, conveniently situated warm room for the maintenance of mosquitos in a constant environment, the cabinet described below was constructed by the authors at a relatively small cost, and set up in a laboratory-class room (35 ft. x 45 ft.). The warm room, being detached and moveable. entailed no structural alterations or installations.