title: A Highly Reactive Geminal P/B Frustrated Lewis Pair: Expanding the Scope to C-X (X=Cl, Br) Bond Activation.
abstract: The geminal frustrated Lewis pair tBu2PCH2B(Fxyl)2(1; Fxyl=3,5-(CF3)2C6H3) is accessible in 65 % yield from tBu2PCH2Li and (Fxyl)2BF. According to NMR spectroscopy and X-ray crystallography, 1 is monomeric both in solution and in the solid state. The intramolecular P⋅⋅⋅B distance of 2.900(5) Å and the full planarity of the borane site exclude any significant P/B interaction. Compound 1 readily activates a broad variety of substrates including H2, EtMe2SiH, CO2/CS2, Ph2CO, and H3CCN. Terminal alkynes react with heterolysis of the C-H bond. Haloboranes give cyclic adducts with strong P-BX3and weak R3B-X bonds. Unprecedented transformations leading to zwitterionic XP/BCX3adducts occur on treatment of 1 with CCl4or CBr4in Et2O. In less polar solvents (C6H6, n-pentane), XP/BCX3adduct formation is accompanied by the generation of significant amounts of XP/BX adducts. FLP 1 catalyzes the hydrogenation of PhCH=NtBu and the hydrosilylation of Ph2CO with EtMe2SiH.
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438, Frankfurt am Main, Germany.
authors.forename: Kamil
authors.initials: K
authors.lastname: Samigullin
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438, Frankfurt am Main, Germany.
authors.forename: Isabelle
authors.initials: I
authors.lastname: Georg
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438, Frankfurt am Main, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Bolte
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438, Frankfurt am Main, Germany.
authors.forename: Hans-Wolfram
authors.initials: HW
authors.lastname: Lerner
authors.affiliation: Institut für Anorganische und Analytische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438, Frankfurt am Main, Germany. Matthias.Wagner@chemie.uni-frankfurt.de.
authors.forename: Matthias
authors.initials: M
authors.lastname: Wagner
keywords: boron; carbon-halogen activation; frustrated Lewis pairs; phosphorus; trihalomethanides
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