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Preparation of Polymer Supported Phosphine Ligands by Metal Catalyzed Living Radical Copolymerization and Their Application to Hydroformylation Catalysis

Authors

  • Dr. Andrés F. Cardozo,

    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4 (France), Fax: (+33) 561553003
    2. CNRS, LGC (Laboratoire de Génie Chimique), 4 Allée Emile Monso, BP 84234, 31030 Toulouse Cedex 4 (France)
    3. Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4 (France)
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  • Dr. Eric Manoury,

    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4 (France), Fax: (+33) 561553003
    2. Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4 (France)
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  • Dr. Carine Julcour,

    1. CNRS, LGC (Laboratoire de Génie Chimique), 4 Allée Emile Monso, BP 84234, 31030 Toulouse Cedex 4 (France)
    2. Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4 (France)
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  • Dr. Jean-François Blanco,

    1. CNRS, LGC (Laboratoire de Génie Chimique), 4 Allée Emile Monso, BP 84234, 31030 Toulouse Cedex 4 (France)
    2. Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4 (France)
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  • Prof. Henri Delmas,

    1. CNRS, LGC (Laboratoire de Génie Chimique), 4 Allée Emile Monso, BP 84234, 31030 Toulouse Cedex 4 (France)
    2. Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4 (France)
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  • Dr. Florence Gayet,

    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4 (France), Fax: (+33) 561553003
    2. Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4 (France)
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  • Prof. Rinaldo Poli

    Corresponding author
    1. CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4 (France), Fax: (+33) 561553003
    2. Université de Toulouse, UPS, INPT, F-31077 Toulouse Cedex 4 (France)
    3. Institut Universitaire de France, 103, bd Saint-Michel, 75005 Paris (France)
    • CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4 (France), Fax: (+33) 561553003
    Search for more papers by this author

Abstract

A series of well-defined polystyrene-supported tertiary phosphine ligands were prepared by copper-catalyzed atom transfer radical polymerization (ATRP), involving direct copolymerization of styrene and 4-diphenylphosphinostyrene (or 4-styryldiphenylphosphine, SDPP). Copolymerization of the two monomers at different molar ratios showed a decreasing level of control as the SDPP molar fraction (fSDPP) increased. A satisfactory level of control was achieved for fSDPP≤0.25 such that there was a constant concentration of growing “living chains”, and linear Mn growth with conversion and low dispersity. Copper-free polymers with different chain lengths were prepared and tested as polymeric ligands in the rhodium-catalyzed hydroformylation of 1-octene. The polymeric ligands yielded higher linear/branched selectivity and lower activity relative to PPh3 at the same P/Rh ratio. The selectivity increased slightly as a function of the polymer chain length.

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