Synthesis, Characterization, and Application of Two Al(ORF)3 Lewis Superacids

Authors

  • Dipl.-Chem. Anne Kraft,

    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • Dr. Nils Trapp,

    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • Dr. Daniel Himmel,

    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • Dipl.-Chem. Hannes Böhrer,

    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • Dipl.-Chem. Peter Schlüter,

    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • Dr. Harald Scherer,

    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • Prof. Dr. Ingo Krossing

    Corresponding author
    1. Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
    • Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Universität Freiburg, Albertstrasse 19, 79104 Freiburg (Germany)
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  • The results on the OC(C5F10)(C6F5)-substituted compounds are part of the Ph.D. thesis of N. Trapp, University of Freiburg, 2008: Novel Salts of Weakly Coordinating Perfluorinated Alkoxyaluminate Anions and their Parent Lewis Acids—Design, Synthesis and Possible Applications, Cuvillier Verlag, Göttingen, 2008.

Abstract

We report herein the synthesis and full characterization of the donor-free Lewis superacids Al(ORF)3 with ORF=OC(CF3)3 (1) and OC(C5F10)C6F5 (2), the stabilization of 1 as adducts with the very weak Lewis bases PhF, 1,2-F2C6H4, and SO2, as well as the internal C[BOND]F activation pathway of 1 leading to Al2(F)(ORF)5 (4) and trimeric [FAl(ORF)2]3 (5, ORF=OC(CF3)3). Insights have been gained from NMR studies, single-crystal structure determinations, and DFT calculations. The usefulness of these Lewis acids for halide abstractions has been demonstrated by reactions with trityl chloride (NMR; crystal structures). The trityl salts allow the introduction of new, heteroleptic weakly coordinating [Cl-Al(ORF)3] anions, for example, by hydride or alkyl abstraction reactions.

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