Efficient Ruthenium Nanocatalysts in Liquid–Liquid Biphasic Hydrogenation Catalysis: Towards a Supramolecular Control through a Sulfonated Diphosphine–Cyclodextrin Smart Combination

The combination between a sulfonated diphosphine (L) and a cyclodextrin (CD) allowed the preparation of very stable water‐soluble ruthenium nanoparticles (RuNPs) that displayed pertinent catalytic performances in hydrogenation of unsaturated substrates with a supramolecular control effect of the cyclodextrin. For comparison purpose, the RuNPs were produced by hydrogenation of the organometallic [Ru(1,5‐cyclooctadiene)(1,3,5‐cyclooctatriene)] complex under mild conditions (3 bar H2; room temperature) and in the presence of L or a L/CD mixture as stabilizer leading to Ru/L and Ru/L/CD systems, respectively. The so‐obtained nanoparticles were fully characterized by complementary techniques. Interestingly, NMR investigations evidenced 1) the strong coordination of the sulfonated diphosphine ligand at the metallic surface and 2) in the presence of cyclodextrin, the formation of an inclusion complex between L and CD that modified the coordination mode of the diphosphine. The investigation of both RuNPs systems in biphasic hydrogenation of unsaturated substrates pointed out relevant differences in terms of reactivity, thus evidencing the influence of the supramolecular interaction at the metallic surface on the catalytic performances of the nanocatalysts. This work took advantage of the supramolecular properties of a cyclodextrin to modulate the surface reactivity of diphosphine‐stabilized ruthenium nanoparticles and may open new opportunities in the field of nanocatalysis.

[1]  K. Philippot,et al.  Methylated β‐Cyclodextrin‐Capped Ruthenium Nanoparticles: Synthesis Strategies, Characterization, and Application in Hydrogenation Reactions , 2013 .

[2]  Chunhua Yan,et al.  A conceptual translation of homogeneous catalysis into heterogeneous catalysis: homogeneous-like heterogeneous gold nanoparticle catalyst induced by ceria supporter. , 2013, Nanoscale.

[3]  K. Philippot,et al.  Palladium catalytic systems with hybrid pyrazole ligands in C–C coupling reactions. Nanoparticles versus molecular complexes , 2013 .

[4]  K. Philippot,et al.  Organometallic Ruthenium Nanoparticles: A Comparative Study of the Influence of the Stabilizer on their Characteristics and Reactivity , 2013 .

[5]  D. González-Gálvez,et al.  NHC-stabilized ruthenium nanoparticles as new catalysts for the hydrogenation of aromatics , 2013 .

[6]  H. Bricout,et al.  Aqueous biphasic hydroformylation in the presence of cyclodextrins mixtures: evidence of a positive synergistic effect. , 2012, Dalton transactions.

[7]  K. Philippot,et al.  Alkyl sulfonated diphosphines-stabilized ruthenium nanoparticles as efficient nanocatalysts in hydrogenation reactions in biphasic media , 2012 .

[8]  L. Bai,et al.  Cyclodextrins as growth controlling agents for enhancing the catalytic activity of PVP-stabilized Ru(0) nanoparticles. , 2012, Chemical communications.

[9]  D. González-Gálvez,et al.  Phosphine-Stabilized Ruthenium Nanoparticles: The Effect of the Nature of the Ligand in Catalysis , 2012 .

[10]  F. Launay,et al.  Chiral ammonium-capped rhodium(0) nanocatalysts: synthesis, characterization, and advances in asymmetric hydrogenation in neat water. , 2012, ChemSusChem.

[11]  F. Launay,et al.  New ammonium surfactant-stabilized rhodium(0) colloidal suspensions: influence of novel counter-anions on physico-chemical and catalytic properties. , 2011, Dalton transactions.

[12]  E. Monflier,et al.  Cyclodextrins and their applications in aqueous-phase metal-catalyzed reactions , 2011 .

[13]  H. Bricout,et al.  Cyclodextrins as Mass Transfer Additives in Aqueous Organometallic Catalysis , 2010 .

[14]  K. Philippot,et al.  Aminopropyltriethoxysilane stabilized ruthenium(0) nanoclusters as an isolable and reusable heterogeneous catalyst for the dehydrogenation of dimethylamine-borane. , 2010, Chemical communications.

[15]  K. Philippot,et al.  An organometallic approach for the synthesis of water-soluble ruthenium and platinum nanoparticles. , 2009, Dalton transactions.

[16]  K. Philippot,et al.  Carbohydrate-derived 1,3-diphosphite ligands as chiral nanoparticle stabilizers: promising catalytic systems for asymmetric hydrogenation. , 2009, ChemSusChem.

[17]  C. Flahaut,et al.  Aqueous hydroformylation reaction mediated by randomly methylated β-cyclodextrin: How substitution degree influences catalytic activity and selectivity , 2009 .

[18]  A. Roucoux,et al.  Catalytically active nanoparticles stabilized by host-guest inclusion complexes in water. , 2009, Chemical communications.

[19]  I. Moreels,et al.  In situ observation of rapid ligand exchange in colloidal nanocrystal suspensions using transfer NOE nuclear magnetic resonance spectroscopy. , 2009, Journal of the American Chemical Society.

[20]  L. Leclercq,et al.  Rhodium-Catalyzed Hydroformylation Promoted by Modified Cyclodextrins: Current Scope and Future Developments , 2008 .

[21]  S. Fourmentin,et al.  Biphasic Aqueous Organometallic Catalysis Promoted by Cyclodextrins: How to Design the Water‐Soluble Phenylphosphane to Avoid Interaction with Cyclodextrin , 2008 .

[22]  K. Philippot,et al.  Reactions of olefins with ruthenium hydride nanoparticles: NMR characterization, hydride titration, and room-temperature C--C bond activation. , 2008, Angewandte Chemie.

[23]  A. Roucoux,et al.  Methylated cyclodextrins: an efficient protective agent in water for zerovalent ruthenium nanoparticles and a supramolecular shuttle in alkene and arene hydrogenation reactions. , 2007, Dalton transactions.

[24]  K. Philippot,et al.  Shape Control of Platinum Nanoparticles , 2007 .

[25]  A. Roucoux,et al.  Supramolecular shuttle and protective agent: a multiple role of methylated cyclodextrins in the chemoselective hydrogenation of benzene derivatives with ruthenium nanoparticles. , 2006, Chemical communications.

[26]  M. El-Sayed,et al.  Chemistry and properties of nanocrystals of different shapes. , 2005, Chemical reviews.

[27]  K. Philippot,et al.  Influence of organic ligands on the stabilization of palladium nanoparticles , 2004 .

[28]  D. Landy,et al.  Molecular Recognition Between a Water‐Soluble Organometallic Complex and a β‐Cyclodextrin: First Example of Second‐Sphere Coordination Adducts Possessing a Catalytic Activity , 2004 .

[29]  H. Bricout,et al.  Cleavage of water-insoluble alkylallylcarbonates catalysed by a palladium/TPPTS/cyclodextrin system: effect of phosphine/cyclodextrin interactions on the reaction rate , 2004 .

[30]  Tapio Salmi,et al.  Gas-phase hydrogenation of o-xylene over Pt/alumina catalyst, activity, and stereoselectivity , 2003 .

[31]  L. Caron,et al.  Thermodynamic insight into the origin of the inclusion of monosulfonated isomers of triphenylphosphine into the beta-cyclodextrin cavity. , 2002, Carbohydrate research.