Synthesis, characterization, and application of two Al(OR(F))3 Lewis superacids |
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Authors: | Kraft Anne Trapp Nils Himmel Daniel Böhrer Hannes Schlüter Peter Scherer Harald Krossing Ingo |
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Institution: | Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF), Universit?t Freiburg, Albertstrasse 19, 79104 Freiburg, Germany. |
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Abstract: | We report herein the synthesis and full characterization of the donor-free Lewis superacids Al(OR(F))(3) with OR(F) = OC(CF(3))(3) (1) and OC(C(5)F(10))C(6)F(5) (2), the stabilization of 1 as adducts with the very weak Lewis bases PhF, 1,2-F(2)C(6)H(4), and SO(2), as well as the internal C-F activation pathway of 1 leading to Al(2)(F)(OR(F))(5) (4) and trimeric FAl(OR(F))(2)](3) (5, OR(F) = OC(CF(3))(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(OR(F))(3)](-) anions, for example, by hydride or alkyl abstraction reactions. |
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