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Synthesis, characterization, and application of two Al(OR(F))3 Lewis superacids.

Authors
  • Kraft, Anne1
  • Trapp, Nils
  • Himmel, Daniel
  • Böhrer, Hannes
  • Schlüter, Peter
  • Scherer, Harald
  • Krossing, Ingo
  • 1 Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF), Universität Freiburg, Albertstrasse 19, 79104 Freiburg, Germany. , (Germany)
Type
Published Article
Journal
Chemistry - A European Journal
Publisher
Wiley (John Wiley & Sons)
Publication Date
Jul 23, 2012
Volume
18
Issue
30
Pages
9371–9380
Identifiers
DOI: 10.1002/chem.201200448
PMID: 22736574
Source
Medline
License
Unknown

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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