Rhodium-Complex-Catalyzed Asymmetric Hydrogenation: Transformation of Precatalysts into Active Species

Authors

  • Angelika Preetz,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381 12 81 51 183
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  • Hans-Joachim Drexler Dr.,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381 12 81 51 183
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  • Christian Fischer,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381 12 81 51 183
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  • Zhenya Dai Dr.,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381 12 81 51 183
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  • Armin Börner Prof. Dr.,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381 12 81 51 183
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  • Wolfgang Baumann Dr.,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381 12 81 51 183
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  • Anke Spannenberg Dr.,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381 12 81 51 183
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  • Richard Thede Priv.-Doz. Dr.,

    1. Institut für Biochemie, Felix-Hausdorff-Strasse 4, 17489 Greifswald, Germany
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  • Detlef Heller Priv.-Doz. Dr.

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany, Fax: (+49) 381 12 81 51 183
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Abstract

The use of diolefin-containing rhodium precatalysts leads to induction periods in asymmetric hydrogenation of prochiral olefins. Consequently, the reaction rate increases in the beginning. The induction period is caused by the fact that some of the catalyst is blocked by the diolefin and thus not available for hydrogenation of the prochiral olefin. Therefore, the maximum reaction rate cannot be reached initially. Due to the relatively slow hydrogenation of cyclooctadiene (cod) the share of active catalysts increases at first, and this leads to typical induction periods. The aim of this work is to quantify the hydrogenation of the diolefins cyclooctadiene (cod) and norborna-2,5-diene (nbd) for cationic complexes of the type [Rh(ligand)(diolefin)]BF4 for the ligands Binap (1,1′-binaphthalene-2,2′-diylbis(phenylphosphine)), Me-Duphos (1,2-bis(2,5-dimethylphospholano)benzene, and Catasium in the solvents methanol, THF, and propylene carbonate. Furthermore, an approach is presented to determine the desired rate constant and the resulting respective pre-hydrogenation time from stoichiometric hydrogenations of the diolefin complexes via UV/Vis spectroscopy. This method is especially useful for very slow diolefin hydrogenations (e.g., cod hydrogenation with the ligands Me-Duphos, Et-Duphos (1,2-bis(2,5-diethylphospholano)benzene), and dppe (1,2-bis(diphenylphosphino)ethane).

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