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Stereospecific Carbene Polymerization with Oxygenated Rh(diene) Species

Authors

  • Annemarie J. C. Walters,

    1. Homogeneous and Supramolecular Catalysis Group, Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)
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  • Dipl.-Chem. Oliver Troeppner,

    1. Lehrstuhl für Bioanorganische Chemie, Department Chemie und Pharmazie, Universität Erlangen-Nürnberg (Germany)
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  • Prof. Dr. Ivana Ivanović-Burmazović,

    1. Lehrstuhl für Bioanorganische Chemie, Department Chemie und Pharmazie, Universität Erlangen-Nürnberg (Germany)
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  • Dr. Cristina Tejel,

    1. C. Tejel, Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) CSIC, Universidad de Zaragoza (Spain)
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  • Dr.  M. Pilar del Río,

    1. Homogeneous and Supramolecular Catalysis Group, Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)
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  • Prof. Dr. Joost N. H. Reek,

    1. Homogeneous and Supramolecular Catalysis Group, Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)
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  • Dr. Bas de Bruin

    Corresponding author
    1. Homogeneous and Supramolecular Catalysis Group, Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)
    • Homogeneous and Supramolecular Catalysis Group, Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands)
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  • Financial support from the European Research Council (ERC, grant agreement 202886-CatCIR), the Netherlands Organization for Scientific Research (NWO-CW), the Dutch Polymer Institute (DPI projects no. 646/647), the University of Amsterdam, the DFG (SFB-583 and Major Research Instrumentation Program) and MICINN/FEDER (Projects CTQ2008-03860 and CTQ2011-22516) is gratefully acknowledged.

Abstract

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Breath-taking activation: Stereoregular carbene polymerization proceeds via cationic [(allyl)RhIII–polymeryl]+ species. These are most efficiently generated by oxygenation of the [(diene)RhI] precatalysts, which involves an unusual rearrangement of 2-rhodaoxetane intermediates. This discovery gives detailed insight in the reaction mechanism.

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