A Highly Reactive Geminal P/B Frustrated Lewis Pair: Expanding the Scope to C-X (X=Cl, Br) Bond Activation.

The geminal frustrated Lewis pair tBu2 PCH2 B(Fxyl)2 (1; Fxyl=3,5-(CF3 )2 C6 H3 ) is accessible in 65 % yield from tBu2 PCH2 Li and (Fxyl)2 BF. 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 , EtMe2 SiH, CO2 /CS2 , Ph2 CO, and H3 CCN. Terminal alkynes react with heterolysis of the C-H bond. Haloboranes give cyclic adducts with strong P-BX3 and weak R3 B-X bonds. Unprecedented transformations leading to zwitterionic XP/BCX3 adducts occur on treatment of 1 with CCl4 or CBr4 in Et2 O. In less polar solvents (C6 H6 , n-pentane), XP/BCX3 adduct 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 Ph2 CO with EtMe2 SiH.