Highly Selective Cobalt-Catalyzed Hydrovinylation of Styrene

Authors

  • Michiel M. P. Grutters,

    1. Schuit Institute of Catalysis, Laboratory of Homogeneous Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands, Fax: (+31)-(0)40-245-5054; phone: (+31)-(0)40-247-2483
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  • Jarl Ivar van der Vlugt,

    1. Schuit Institute of Catalysis, Laboratory of Homogeneous Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands, Fax: (+31)-(0)40-245-5054; phone: (+31)-(0)40-247-2483
    2. Current address: van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, the Netherlands
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  • Yuxin Pei,

    1. Department of Organic Chemistry, Royal Institute of Technology (KTH), Stockholm, Sweden
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  • Allison M. Mills,

    1. Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University, 3584 CH Utrecht, The Netherlands
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  • Martin Lutz,

    1. Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University, 3584 CH Utrecht, The Netherlands
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  • Anthony L. Spek,

    1. Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University, 3584 CH Utrecht, The Netherlands
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  • Christian Müller,

    1. Schuit Institute of Catalysis, Laboratory of Homogeneous Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands, Fax: (+31)-(0)40-245-5054; phone: (+31)-(0)40-247-2483
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  • Christina Moberg,

    1. Department of Organic Chemistry, Royal Institute of Technology (KTH), Stockholm, Sweden
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  • Dieter Vogt

    1. Schuit Institute of Catalysis, Laboratory of Homogeneous Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands, Fax: (+31)-(0)40-245-5054; phone: (+31)-(0)40-247-2483
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Abstract

Phosphine complexes of cobalt halide salts activated by diethylaluminum chloride are shown to yield highly active catalysts in the hydrovinylation of styrene, with unprecedented high selectivity to the desired product 3-phenyl-1-butene (3P1B). Double-bond isomerization, a common problem in codimerization reactions, only occurs after full conversion with these catalyst systems, even at elevated temperature. The most active catalysts are based on cobalt halide species combined with either C1- or C2-bridged diphosphines, heterodonor P,N or P,O ligands, flexible bidentate phosphine ligands or monodentate phosphine ligands. Kinetic investigations show an order >1 in catalyst, which indicates either the involvement of dinuclear species in the catalytic cycle or partial catalyst decomposition via a bimolecular pathway.

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