Organometallic synthesis of water-soluble ruthenium nanoparticles in the presence of sulfonated diphosphines and cyclode
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Organometallic synthesis of water-soluble ruthenium nanoparticles in the presence of sulfonated diphosphines and cyclodextrins Miguel Guerrero,1 Nguyet Trang Thanh Chau,2 Alain Roucoux,2 Audrey Nowicki-Denicourt,2 Eric Monflier,3 Hervé Bricout3 and Karine Philippot*1 1 CNRS; LCC (Laboratoire de Chimie de Coordination); 205 Route de Narbonne, F-31077 Toulouse, France; Université de Toulouse; UPS, LCC; F-31077 Toulouse; France. 2 Ecole Nationale Supérieure de Chimie de Rennes, UMR, CNRS 6226, Avenue du General Leclerc, CS 50837, 35 708 RENNES Cedex 7; Université Européenne de Bretagne; France. 3 UMR CNRS 8181; Université d'Artois, Rue Jean Souvraz, F-62307 Lens Cedex; France.
*Corresponding author; E-mail address: [email protected] ABSTRACT The organometallic approach was successfully applied to synthesize water-soluble ruthenium nanoparticles displaying interesting catalytic properties in hydrogenation of unsaturated model-substrates. Nanocatalyst synthesis was performed by hydrogenation of the complex [Ru(COD)(COT)] in the presence of sulfonated diphosphines and cyclodextrins as protective agents providing very small ruthenium nanoparticles (ca. 1.2-1.5 nm) with narrow size distribution and high stability. Catalysis results in water evidenced a control of the surface properties of these novel ruthenium nanocatalysts at a supramolecular level.
INTRODUCTION Since the end of the 1990s, and with the development of nanosciences, nanocatalysis has clearly emerged as a domain at the interface between homogeneous and heterogeneous catalysis, which offers unique solutions to answer the demanding conditions for catalyst improvement.[1,2] A modern approach of colloidal chemistry is presently being developed to increase the reactivity of nanoparticles in a limited size up to 10 nm, using several types of capping agents.[3] Among others the organometallic approach represents an efficient synthetic methodology to get well-controlled metallic nanoparticles in terms of size and composition, two key-parameters for application in nanocatalysis.[4] Various metal organic complexes can be used as metal source, being decomposed under mild conditions of solution chemistry, to provide mono- and bimetallic systems. This approach is also versatile in terms of stabilizing agents since polymers, ligands, ionic liquids or inorganic supports (alumina, silica, carbone derivatives, etc) can be used. The choice of the stabilizer is critical as it will govern nanoparticle characteristics as their size, shape, dispersion, surface properties and further, influence their catalytic properties. In this context, choosing ligands as those used in organometallic chemistry and catalysis is thus of interest since one can expect to tune the surface properties of metal nanoparticles as performed with molecular complexes. This can be even applied to obtain water-soluble nanoparticles while starting their synthesis in organic medium as firstly evidenced using 1,3,5-triaza-7-
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phosphaadamantane (PTA) for the preparation of platinum and ruthe
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