A Cooperative Rhodium/Secondary Phosphine Oxide [Rh/P(O)nBu2] Template for Catalytic Hydrodefluorination of Perfluoroarenes |
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Authors: | Wei-Chieh Chang Helena Randel Thomas Weyhermüller Alexander A. Auer Christophe Farès Christophe Werlé |
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Affiliation: | 1. Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34–36, 45470 Mülheim an der Ruhr, Germany;2. Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der, Ruhr, Germany |
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Abstract: | The selective activation of C−F bonds under mild reaction conditions remains an ongoing challenge of bond activation. Here, we present a cooperative [Rh/P(O)nBu2] template for catalytic hydrodefluorination (HDF) of perfluoroarenes. In addition to substrates presenting electron-withdrawing functional groups, the system showed an exceedingly rare tolerance for electron-donating functionalities and heterocycles. The high chemoselectivity of the catalyst and its readiness to be deployed at a preparative scale illustrate its practicality. Empirical mechanistic studies and a density functional theory (DFT) study have identified a rhodium(I) dihydride complex as a catalytically relevant species and the determining role of phosphine oxide as a cooperative fragment. Altogether, we demonstrate that molecular templates based on these design elements can be assembled to create catalysts with increased reactivity for challenging bond activations. |
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Keywords: | Cooperative Template Homogeneous Catalysis Hydrodefluorination Rhodium Secondary Phosphine Oxide |
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