Ruthenium Trichloride Catalyst in Water: Ru Colloids versus Ru Dimer Characterization Investigations.

An easy-to-prepare ruthenium catalyst obtained from ruthenium(III) trichloride in water demonstrates efficient performances in the oxidation of several cycloalkanes with high selectivity toward the ketone. In this work, several physicochemical techniques were used to demonstrate the real nature of the ruthenium salt still unknown in water and to define the active species for this Csp3-H bond functionalization. From transmission electron microscopy analyses corroborated by SAXS analyses, spherical nanoobjects were observed with an average diameter of 1.75 nm, thus being in favor of the formation of reduced species. However, further investigations, based on X-ray scattering and absorption analyses, showed no evidence of the presence of a metallic Ru-Ru bond, proof of zerovalent nanoparticles, but the existence of Ru-O and Ru-Cl bonds, and thus the formation of a water-soluble complex. The EXAFS (extended X-ray absorption fine structure) spectra revealed the presence of an oxygen-bridged diruthenium complex [Ru(OH) xCl3- x]2(µ-O) with a high oxidation state in agreement with catalytic results. This study constitutes a significant advance to determine the true nature of the RuCl3·3H2O salt in water and proves once again the invasive nature of the electron beam in microscopy experiments, routinely used in nanochemistry.

Odyssey in Polyphasic Catalysis by Metal Nanoparticles.

Nanometer-sized metal particles constitute an unavoidable family of catalysts, combining the advantages of molecular complexes in regards to their catalytic performances and the ones of heterogeneous systems in terms of easy recycling. As part of this research, our group aims at designing well-defined metal nanoparticles based-catalysts, in non-conventional media (ionic liquids or water), for various catalytic applications (hydrogenation, dehalogenation, carbon-carbon coupling, asymmetric catalysis) in mild reaction conditions. In the drive towards a more eco-responsible chemistry, the main focuses rely on the search of highly active and selective nanocatalysts, in association with an efficient recycling mainly under pure biphasic liquid-liquid conditions. In this Personal Account, we proposed our almost fifteen-years odyssey in the world of metal nanoparticles for a sustainable catalysis.

Calcium trifluoroacetate as an efficient catalyst for ring-opening of epoxides by amines under solvent-free conditions.

Ca(CF3CO2)2 efficiently catalyzed the selective ring-opening of epoxides by amines leading to the synthesis of ß-aminoalcohols. The reaction works well with various aromatic and aliphatic amines under solvent-free conditions. Corresponding ß-aminoalcohols were obtained in excellent yields with high regioselectivity. The catalyst was easily prepared by reaction of CaH2 in trifluoroacetic acid.

N-donor ligands based on bipyridine and ionic liquids: an efficient partnership to stabilize rhodium colloids. Focus on oxygen-containing compounds hydrogenation.

Polynitrogen ligands and/in ionic liquids (ILs) are described as a pertinent tandem to efficiently stabilize rhodium nanoparticles (NPs) in the size range of 2.0 nm for catalytic applications. Several N-donor ligands based on bipyridine skeleton were used as extra protective agents in [BMI][PF(6)] and compared in the hydrogenation of functionalized aromatic compounds at 80 °C and under 40 bar H(2). The nature of the bipyridine derivative and its influence on the coordination mode on the particle surface were proposed to explain the observed different kinetic properties. The hydrogenation of various oxygen-containing arenes was investigated and original results were described in the reduction of anisole and cresols as model lignin compounds, providing a significant ratio of ketone derivatives. A first explanation based on possible reaction routes is proposed to justify the formed products.

Catalytically active nanoparticles stabilized by host-guest inclusion complexes in water.

Hydrogenation of arene derivatives can be successfully performed in water by using ruthenium(0) nanoparticles stabilized by 1 : 1 inclusion complexes formed between methylated cyclodextrins and an ammonium salt bearing a long alkyl chain.

A surfactant-assisted preparation of well dispersed rhodium nanoparticles within the mesopores of AlSBA-15: characterization and use in catalysis.

Well dispersed and efficient Rh(0) hydrogenation catalysts were obtained by the reduction of Rh(III)-exchanged mesoporous aluminosilicates by sodium borohydride in the presence of N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl) ammonium chloride.

Diphosphite ligands derived from carbohydrates as stabilizers for ruthenium nanoparticles: promising catalytic systems in arene hydrogenation.

Ruthenium nanoparticles (RuNPs) were prepared through the hydrogenation of [Ru(COD)(COT)] (COD = 1,5-cyclooctadiene, COT = 1,3,5-cyclooctatriene) in the presence of diphosphites derived from carbohydrates as stabilizing agents, and interestingly, structural modifications of the diphosphite backbone were found to influence nanoparticle size and dispersity, as well as their catalytic activity in arene hydrogenation.

Rhodium nanocatalysts stabilized by various bipyridine ligands in nonaqueous ionic liquids: influence of the bipyridine coordination modes in arene catalytic hydrogenation.

Rhodium nanoparticles stabilized by 2,2'-, 3,3'-, 4,4'-bipyridine ligands were prepared in various ionic liquids according to a chemical reduction approach. Zerovalent nanospecies in the size range of 2.0-2.5 nm were characterized. The nature of the bipyridine and its influence on the coordination environment of rhodium nanoparticles were investigated in various nonaqueous ionic liquids according to the cation and anion. The hydrogenation of various aromatic compounds by these colloidal suspensions was carried out at 80 degrees C and under 40 bar of H 2. A first structural explanation based on bipyridine coordination modes is proposed to justify the observed different activities.

Supramolecular shuttle and protective agent: a multiple role of methylated cyclodextrins in the chemoselective hydrogenation of benzene derivatives with ruthenium nanoparticles.

Efficient chemoselectivities have been obtained in the hydrogenation of benzene derivatives under biphasic liquid-liquid conditions using Ru(0) nanoparticles stabilized and controlled by the relevant choice of cavity and methylation degree of cyclodextrins.

Organic phase stabilization of rhodium nanoparticle catalyst by direct phase transfer from aqueous solution to room temperature ionic liquid based on surfactant counter anion exchange.

We describe the organic phase transfer of surfactant-stabilized rhodium nanoparticles previously synthesized in an aqueous solution of N,N-dimethyl-N-dodecyl-N-(2-hydroxyethyl)ammonium chloride (HEA12Cl); the addition of LiN(Tf)2 to the aqueous suspension of Rh-HEA12Cl transferred the hydrosol nanoparticles to an ionic liquid phase.

Development of 99mTc labelled Lipiodol: biodistribution following injection into the hepatic artery of the healthy pig.

BACKGROUND: We develop a method for the radiolabelling of Lipiodol with Tc, using a lipophilic complex, [99mTc-(S2CPh)(S3Ph)2], dissolved in Lipiodol (99mTc-SSS Lipiodol). RESULTS: The labelling yield is high (96 +/- 0.8%), and the radiochemical purity satisfactory (92 +/- 2.6%). This labelling is reproducible and stable for up to 24 h in vitro. Studies carried out after injection into the hepatic artery of the healthy pig show that the biodistribution of 99mTc-SSS Lipiodol is comparable with that observed for 188Re Lipiodol. MATERIALS AND METHODS: The 99mTc-SSS lipiodol was obtained after dissolving a chelating agent, previously labelled with 99mTc, in cold lipiodol. The radiochemical purity (RCP) of the labelling was checked immediately and at 24 h. The 99mTc-SSS lipiodol was injected into the hepatic artery of four healthy pigs for an ex-vivo biodistribution study. An autoradiographic study was performed in two cases. CONCLUSIONS: Apart from the specific interest of a Lipiodol-bearing technetiated agent for carrying out dosimetric studies, the labelling of Lipiodol with 99mTc is a preliminary step towards the use of radiolabelling with the 188Re analogue.

Cyclodextrins as growth controlling agents for enhancing the catalytic activity of PVP-stabilized Ru(0) nanoparticles.

Cyclodextrins act as growth controllers in the synthesis of PVP-stabilized Ru(0) nanoparticles, leading to enhancement of the catalytic activity in the hydrogenation of furfural.

Chiral ammonium-capped rhodium(0) nanocatalysts: synthesis, characterization, and advances in asymmetric hydrogenation in neat water.

Optically active amphiphilic compounds derived from N-methylephedrine, N-methylprolinol, or cinchona derivatives possessing bromide or chiral lactate counterions were efficiently used as protective agents for rhodium(0) nanoparticles. The full characterization of these surfactants and the obtained nanocatalysts was performed by means of different techniques. These spherical nanoparticles, with sizes between 0.8-2.5 nm depending on the stabilizer, were evaluated in the hydrogenation of model substrates in neat water as a green solvent. The rhodium catalysts showed relevant kinetic properties, but modest enantiomeric excess values of up to 13 % in the hydrogenation of ethyl pyruvate. They were also investigated in the hydrogenation of disubstituted arenes, such as m-methylanisole, providing interesting catalytic activities and a preferential cis selectivity of around 80 %; however, no asymmetric induction was observed.

New ammonium surfactant-stabilized rhodium(0) colloidal suspensions: influence of novel counter-anions on physico-chemical and catalytic properties.

Novel anionic species, such as hydrogen carbonate (HCO(3)(−)), fluoride (F(−)), triflate (CF(3)SO(3)(−)), tetrafluoroborate (BF(4)(−)) and chloride (Cl(−)) were investigated as new partners of water soluble N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl) ammonium salts, used as a protective agent of rhodium colloids. The effect of the surfactant polar head on the micellar behavior, size and morphology of the nanospecies was studied by adapted physico-chemical experiments (surface tension measurements, dynamic light scattering, thermogravimetric and TEM analyses) and discussed in terms of strong or weak stabilization of the growing nanoparticles surface. Finally, the influence of the nanoenvironment generated by the surfactant with various counter-anions was evaluated via the hydrogenation of aromatics.

Using click chemistry to access mono- and ditopic ß-cyclodextrin hosts substituted by chiral amino acids.

A wide range of chiral mono- and ditopic cyclodextrin-based receptors have been synthesized by CuI-catalyzed azide-alkyne cycloaddition starting from mono-6-azido-ß-cyclodextrin and chiral amino acids. Of interest, microwaves proved very efficient to access a wide range of ditopic ß-cyclodextrin receptors with quantitative yields.

Polyhydroxylated ammonium chloride salt: a new efficient surfactant for nanoparticles stabilisation in aqueous media. Characterization and application in catalysis.

A trihydroxyammonium chloride has proved to be an efficient protective agent for Rh(0) nanoparticles and the hydrogenation of arene compounds has been investigated. Significant formation of cyclohexanone in the reduction of anisole has been demonstrated.

Carbohydrate-derived 1,3-diphosphite ligands as chiral nanoparticle stabilizers: promising catalytic systems for asymmetric hydrogenation.

Metallic Ru, Rh, and Ir nanoparticles were prepared by the decomposition of organometallic precursors under H(2) pressure in the presence of 1,3-diphosphite ligands, derived from carbohydrates, as stabilizing agents. Structural modifications to the diphosphite backbone were found to influence the nanoparticles' size, dispersion, and catalytic activity. In the hydrogenation of o- and m-methylanisole, the Rh nanoparticles showed higher catalytic activity than the corresponding Ru nanoparticles. The Ir nanoparticles presented the lowest catalytic activity of the series. In all cases, the hydrogenation of o-methylanisole gave total selectivity for the cis-product, however, the ee of the product was always less than 6 %. A maximum of 81 % cis-selectivity was obtained for the hydrogenation of m-methylanisole, however, no asymmetric induction was observed. These results show that the catalytic activity is affected by a combination of influences from the substrate, the diphosphite ligands, and the metallic nanoparticles.

Methylated cyclodextrins: an efficient protective agent in water for zerovalent ruthenium nanoparticles and a supramolecular shuttle in alkene and arene hydrogenation reactions.

Zerovalent ruthenium(0) nanoparticles in the size range of 2.5 nm were easily prepared by chemical reduction of ruthenium salt with an excess amount of sodium borohydride and were efficiently stabilized by methylated cyclodextrins. The optimization of the catalytic system has been carried out in terms of stability and catalytic activity, considering the hydrogenation of olefinic compounds under biphasic liquid-liquid conditions. Efficient and controlled chemoselectivities were obtained in the hydrogenation of arene derivatives by the relevant choice of cavity and methylation degree of the cyclodextrins. Finally, the hydrogenation of alpha- and beta-pinenes leads to the major formation of cis-pinanes, interesting synthons for fine chemistry, with high diastereoisomeric excesses.

Chelated hydrazido(3-)rhenium(V) complexes: on the way to the nitrido-M(V) core (M = Tc, Re).

Neutral and asymmetrical hydrazido(3-)rhenium(V) heterocomplexes of the type [Re(eta(2)-L(4))(L(n))(PPh(3))] (eta(2)-L(4) = NNC(SCH(3))S; H(2)L(1) = S-methyl beta-N-((2-hydroxyphenyl)ethylidene)dithiocarbazate, 1, H(2)L(2) = S-methyl beta-N-((2-hydroxyphenyl)methylidene)dithiocarbazate, 2) are prepared via ligand-exchange reactions in ethanolic solutions starting from [Re(V)(O)Cl(4)](-) in the presence of PPh(3) or from [Re(V)(O)Cl(3)(PPh(3))(2)]. The distorted octahedral coordination sphere of these compounds is saturated by a chelated hydrazido group, a facially ligated ONS Schiff base, and PPh(3). Reduction-substitution reactions starting from [NH(4)][Re(VII)O(4)] in acidic ethanolic mixtures containing PPh(3) and H(2)L(n) (or its dithiocarbazic acid precursor H(3)L(4)) produce another example of chelated hydrazido(3-) rhenium(V) derivative, namely [Re(eta(2)-L(4))Cl(2)(PPh(3))(2)], 3. On the contrary, the N-methyl-substituted dithiocarbazic acid H(2)L(3) reacts with perrhenate to give the known nitrido complex [Re(N)Cl(2)(PPh(3))(2)]. Rhenium(V) complexes incorporating the robust eta(2)-hydrazido moiety represent key intermediates helpful for the comprehension of the reaction pathway which generates nitridorhenium(V) species starting from oxo precursors. An essential requirement for the stabilization of such chelated hydrazido-Re(V) units is the triple deprotonation at the hydrazine nitrogens, thereby providing efficient pi-electron circulation in the resulting five-membered ring. The thermal stability of these units is affected by the nature of the anchoring donor, thione sulfur ensuring stronger chelation than nitrogen and oxygen. The eta(2)-hydrazido complexes are characterized by conventional physicochemical techniques, including the X-ray crystal structure determination of 1 and 3.