Catalysis Today 156 (2010) 268–275 Contents lists available at ScienceDirect Catalysis Today journal homepage: www.elsevier.com/locate/cattod Immobilisation of an ionically tagged Hoveyda catalyst on a supported ionic liquid membrane: An innovative approach for metathesis reactions in a catalytic membrane reactor A. Keraani a,c , M. Rabiller-Baudry a,c,∗ , C. Fischmeister b,c,∗∗ , C. Bruneau b,c a Université Rennes 1, UMR « Sciences Chimiques de Rennes » CNRS - équipe Chimie et Ingénierie des Procédés, 263 avenue du Général Leclerc, CS 74205, case 1011, 35042 Rennes cedex, France b CNRS, UMR « Sciences Chimiques de Rennes » - Université Rennes 1- équipe Catalyse et Organométalliques, 263 avenue du Général Leclerc, CS 74205, case 1011, 35042 Rennes cedex, France c Université Européenne de Bretagne, France article info Article history: Keywords: Nanofiltration Metathesis Ionic liquid Immobilisation Catalytic membrane reactor abstract This study aimed at developing an innovative strategy to recycle homogeneous olefin metathesis catalysts by the combination of complementary green processes, namely organic solvent nanofiltration coupled with ionic liquid advantages. The immobilisation of an ionically tagged Hoveyda catalyst in an ionic liquid previously supported on a solvent-resistant polyimide membrane (Starmem 228) was prepared leading to an original catalytic membrane successfully used in a membrane reactor for a model metathesis reaction. © 2010 Elsevier B.V. All rights reserved. 1. Introduction Ruthenium-catalysed olefin metathesis reactions represent a powerful method for the formation of carbon–carbon double bonds allowing synthesis of various intermediate compounds useful for fine chemistry [1–8]. Among catalysts based on ruthenium, Hov- eyda catalysts [9–11] are well known to be stable homogeneous metathesis catalysts used at laboratory scale. These catalysts have demonstrated their abilities to perform extremely selective organic syntheses with high yields. Nevertheless, only few industrial pro- cesses use metathesis reactions owing to the cost of homogeneous ruthenium-catalysts together with difficulties of final separation of the catalysts from the reaction media and their subsequent recycling. To overcome this major problem limiting industrial development, immobilisation of the Hoveyda catalysts in biphasic systems using ionic liquids (IL) is an attractive approach for the sep- aration and recycling [12–16]. However, biphasic IL-organic solvent ∗ Corresponding author at: Université Rennes 1, UMR « Sciences Chimiques de Rennes » CNRS - équipe Chimie et Ingénierie des Procédés, 263 avenue du Général Leclerc, CS 74205, case 1011, 35042 Rennes cedex, France. ∗∗ Corresponding author at: CNRS, UMR « Sciences Chimiques de Rennes » - Uni- versité Rennes 1- équipe Catalyse et Organométalliques, 263 avenue du Général Leclerc, CS 74205, case 1011, 35042 Rennes cedex, France. E-mail addresses: murielle.rabiller-baudry@univ-rennes1.fr (M. Rabiller-Baudry), cedric.fischmeister@univ-rennes1.fr (C. Fischmeister). systems induce mass transport limitations due to IL high viscosity and require large amounts of sometimes expensive ionic liquids [17,18]. Moreover, the reaction products are generally removed from the IL by solvent extraction, reducing the environmental benefits claimed for ILs but with a remaining attractivity thanks to the possible enhancement of the catalytic performances [19]. Recently, a new approach using the concept of supported ionic liquid phase (SILP) has been developed as an alternative to pure biphasic systems which consist in the immobilisation of a cata- lyst into an ionic liquid supported on a solid phase [20–22]. This approach reduces the amount of ionic liquid required and can over- come mass transport limitation. SILP technology has been used in various reactions such as hydroformylation [23,24], Friedel–Crafts acylations [25], Suzuki cross-coupling [26,27], allylic substitu- tion [28], Heck reaction [29] and hydrogenation [30] using a broad range of solid phases such as silica [20,24,25,29,31], alu- mina [23,27], MFI zeolite [26], chitosan [28] and carbon nanotubes [32]. Even though the necessity to recycle homogeneous organometallic catalysts is commonly accepted, the applied separation technique has to be selected with an eco-design objective. Indeed, the separation steps represent up to 70% of the operating costs of a manufactured product and participate as much as 45% of its global energy cost [33]. Organic Solvent NanoFiltration (OSNF) is a recent process that allows separation of organic mixtures at molecular level by applying a pressure 0920-5861/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.cattod.2010.04.024