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A Fast-Initiating Ionically Tagged Ruthenium Complex: A Robust Supported Pre-catalyst for Batch-Process and Continuous-Flow Olefin Metathesis

Authors

  • Dr. Etienne Borré,

    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108
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  • Dr. Mathieu Rouen,

    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108
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  • Isabelle Laurent,

    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108
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  • Magaly Magrez,

    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108
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  • Dr. Fréderic Caijo,

    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108
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  • Dr. Christophe Crévisy,

    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108
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  • Dr. Wladimir Solodenko,

    1. Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1B, 30167 Hannover (Germany), Fax: (+49) 511-7623011
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  • Loic Toupet,

    1. Institut de Physique de Rennes Université Rennes 1, CNRS, UMR 6251 - Campus de Beaulieu, Bâtiment 11A 263 Av. Général Leclerc, 35042 Rennes Cedex (France)
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  • René Frankfurter,

    1. Institut für Anorganische Chemie, Leibniz Universität Hannover Callinstrasse 1, D-30167 Hannover (Germany)
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  • Prof. Dr. Carla Vogt,

    1. Institut für Anorganische Chemie, Leibniz Universität Hannover Callinstrasse 1, D-30167 Hannover (Germany)
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  • Prof. Dr. Andreas Kirschning,

    Corresponding author
    1. Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1B, 30167 Hannover (Germany), Fax: (+49) 511-7623011
    • Andreas Kirschning, Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1B, 30167 Hannover (Germany), Fax: (+49) 511-7623011===

      Marc Mauduit, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108===

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  • Dr. Marc Mauduit

    Corresponding author
    1. Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108
    • Andreas Kirschning, Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1B, 30167 Hannover (Germany), Fax: (+49) 511-7623011===

      Marc Mauduit, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Av. du Général Leclerc, CS 50837, 35708 Rennes Cedex 7 (France), Fax: (+33) 223238108===

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Abstract

In this study, a new pyridinium-tagged Ru complex was designed and anchored onto sulfonated silica, thereby forming a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions. The involvement of an oxazine–benzylidene ligand allowed the reactivity of the formed Ru pre-catalyst to be efficiently controlled through both steric and electronic activation. The oxazine scaffold facilitated the introduction of the pyridinium tag, thereby affording the corresponding cationic pre-catalyst in good yield. Excellent activities in ring-closing (RCM), cross (CM), and enyne metathesis were observed with only 0.5 mol % loading of the pre-catalyst. When this powerful pre-catalyst was immobilized onto a silica-based cationic-exchange resin, a versatile catalytically active material for batch reactions was generated that also served as fixed-bed material for flow reactors. This system could be reused at 1 mol % loading to afford metathesis products in high purity with very low ruthenium contamination under batch conditions (below 5 ppm). Scavenging procedures for both batch and flow processes were conducted, which led to a lowering of the ruthenium content to as little as one tenth of the original values.

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