Mechanistic Insights into a Supramolecular Self-Assembling Catalyst System: Evidence for Hydrogen Bonding during Rhodium-Catalyzed Hydroformylation

Authors

  • Urs Gellrich,

    1. Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg i. Brsg. (Germany)
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  • Dr. Wolfgang Seiche,

    1. Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg i. Brsg. (Germany)
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  • Dr. Manfred Keller,

    1. Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg i. Brsg. (Germany)
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  • Prof. Dr. Bernhard Breit

    Corresponding author
    1. Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg i. Brsg. (Germany)
    • Institut für Organische Chemie und Biochemie, Freiburg Institute for Advanced Studies (FRIAS), Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg i. Brsg. (Germany)
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  • Support from the Freiburg Institute for Advanced Studies (FRIAS), the Deutsche Forschungsgemeinschaft (IRTG 1038), and the Fonds der chemischen Industrie (PhD fellowship to U.G.) is gratefully acknowledged. We thank S. Diezel for support with the kinetic experiments, J. Schäfer for help with X-ray structure analysis, and Dr. M. Cooke and Prof. Dr. D. Plattner for stimulating discussions.

Abstract

original image

The structural integrity and flexibility provided by intermolecular hydrogen bonds leads to the outstanding properties of the 6-diphenylphosphinopyridin-(2H)-1-one ligand (see scheme) in the rhodium-catalyzed hydroformylation of terminal alkenes, as demonstrated by the combination of spectroscopic methods and DFT computations. Hydrogen bonds were also detected in a competent intermediate of the catalytic cycle.

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