Alcohols, in particular polyols, are well-known for the synthesis of metal nanoparticles often acting as reducing agents, solvents, and stabilizers. Given not only their structural flexibility depending on the number of OH functions and their inherent H bonding interactions, but also the wide range of polyol molecular weights readily available, different physico-chemical properties (boiling point, polarity, viscosity) could be exploited towards the synthesis of well-defined nanomaterials. In particular, the relevance of the supramolecular structure of polyols has a fundamental impact on the formation of metal nanoparticles thereby favoring the dispersion of the nanoclusters. In the field of the metal-based nanocatalysis, palladium occupies a privileged position mainly due to its remarkable versatility in terms of reactivity representing a foremost tool in synthesis. In this review, we describe the controlled synthesis of Pd-based nanoparticles in polyol medium focusing on the progress in terms of tailoring size, morphology, structure, and surface state. Moreover, we discuss the use of 4.2. C(sp)-C(sp 2) Sonogashira cross-coupling 4.3. C(sp 2)-C(sp 2) Hiyama-Denmark cross-coupling 4.4. C(sp 2)-C(sp 2) Heck-Mizoroki cross-coupling 4.5. C(sp 2)-C(sp 2 /sp 3) Suzuki-Miyaura cross-coupling 4.5.1. In PEG and glycerol media 4.5.2. Solid-supported nanocatalysts 4.6. C(sp 2)-C(sp 2)-C(sp 2) Carbonylative Suzuki cross-coupling 4.7. C(sp 2)-C(sp 2) Ullmann-type homo-coupling 4.8. Miscellaneous: SiN and C-N amination reactions 5. Conclusions and outlook

Tin(IV) trifluoromethanesulfonate has been found to be an excellent catalyst for the cycloisomerisation of non-activated and differently substituted olefinic alcohols to cyclic ethers.

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We report in this paper the stabilization of ruthenium nanoparticles using a very simple ligand (4-(3-phenylpropyl)pyridine), through strong pi-coordination of the phenyl moiety.

The hybrid imine/amine palladium(II) coordination complexes [PdX2(kappa2-N(imino),N(amino))](X = Cl, AcO; kappa2-N(imino),N(amino)= 4ClC6H4CHNCH2(CH2)nN(CH3)2, n= 1, 2) have been prepared in different isomeric forms which include E/Z arrangement around the C[double bond]N bond of the hybrid ligand and {Pd(kappa(2)-N(imino),N(amino))} ring conformation. The crystal structures of four of them, E-1AcO, Z-1AcO, E-2AcO and E-2Cl, have been determined and the solution behaviour in acetic acid, the common cyclometallating solvent, for all these systems studied. The complexes in acetic acid solution are shown to maintain the structure determined by X-ray crystallography, as they do in deuterated chloroform. Nevertheless, a partial opening equilibrium of the {Pd(kappa2-N(imino),N(amino))} ring is observed by NMR experiments. When the complexes are held in solution for longer periods the corresponding cyclometallated derivatives, 1AcO-CM, 2AcO-CM, 1Cl-CM and 2Cl-CM, containing the {Pd(kappa2-C,N(imino))} palladacycle are obtained, as characterized by 1H NMR spectroscopy. In these compounds the total opening of the N(amino) moiety of the ligand has occurred. The C-H bond activation process has been studied kinetico-mechanistically at different temperatures, pressures and acid concentrations; the results agree with the need of an opening of the chelate ring in [PdX2(kappa2-N(imino),N(amino))] prior to the proper cyclometallation reaction. The values of the enthalpies of activation are higher than those observed for known N-monodentated cyclometallating ligands, as should correspond to the contribution of a ligand dechelation pre-equilibrium. The entropies and volumes of activation are also indicative of this predissociation that include an important amount of contractive ordering. The presence of small amounts of triflic acid in the reaction medium accelerates the reaction to the value observed for N(imino)-monodentate systems, indicating that the full opening of the chelate ring has taken place. For the badly oriented isomeric forms of the ligand in the chelated complex (Z), the cyclometallation process is even more slow and corresponds directly to the reorganization of the ligand to its cyclopalladation-active (E) conformation.

International audienceThe elaboration of a polymeric catalytic membrane containing palladium nanoparticles is presented. The membrane was prepared using a photo-grafting process with imidazolium-based ionic liquid monomers as modifying agent and microPES® as support membrane. Ionic liquid serves as a stabilizer and immobilizer for the catalytic species, i.e. palladium nanoparticles. The Suzuki–Miyaura cross-coupling reaction was carried out on the catalytic membrane in flow-through configuration. Complete conversion was achieved in 10 s through one single filtration, without formation of byproducts. The apparent reaction rate constant was three orders of magnitude greater than in a batch reactor. No catalyst leaching was detected. This membrane offers the possibility of continuous production with no need for a separation step of the catalyst from the reaction medium

Bimetallic nanoparticles represent attractive catalytic systems thanks to the synergy between both partners at the atomic level, mainly induced by electronic effects which in turn are associated with the corresponding structures (alloy, core-shell, hetero-dimer). This type of engineered material can trigger changes in the kinetics of catalyzed processes by variations on the electrophilicity/nucleophilicity of the metal centers involved and also promote cooperative effects to foster organic transformations, including multi-component and multi-step processes. Solvents become a crucial factor in the conception of catalytic processes, not only due to their environmental impact, but also because they can preserve the bimetallic structure during the catalytic reaction and therefore increase the catalyst lifetime. In this frame, the present review focuses on the recent works described in the literature concerning the synthesis of bimetallic nanoparticles in non-conventional solvents, i.e., other than common volatile compounds, for catalytic applications.

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