TY  - JOUR
A1  - Samigullin, Kamil
A1  - Georg, Isabelle
A1  - Bolte, Michael
A1  - Lerner, Hans-Wolfram
A1  - Wagner, Matthias
T1  - A highly reactive geminal P/B frustrated Lewis pair: expanding the scope to C−X (X=Cl, Br) bond activation
T2  - Chemistry
N2  - 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−BX3 and weak R3B−X bonds. Unprecedented transformations leading to zwitterionic XP/BCX3 adducts occur on treatment of 1 with CCl4 or CBr4 in Et2O. In less polar solvents (C6H6, 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 Ph2CO with EtMe2SiH.
Y1  - 2016
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/42246
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-422469
SN  - 0947-6539
N1  - http://creativecommons.org/licenses/by-nc-nd/4.0/
VL  - 22
IS  - 10
SP  - 3478
EP  - 3484
PB  - Wiley-VCH
CY  - Weinheim
ER  -