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 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.

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Author:Kamil Samigullin, Isabelle Georg, Michael BolteORCiD, Hans-Wolfram LernerORCiDGND, Matthias WagnerORCiD
Parent Title (English):Chemistry
Place of publication:Weinheim
Document Type:Article
Date of Publication (online):2016/11/26
Date of first Publication:2016/02/02
Publishing Institution:Universitätsbibliothek Johann Christian Senckenberg
Release Date:2016/12/21
Page Number:7
First Page:3478
Last Page:3484
Institutes:Biochemie, Chemie und Pharmazie / Biochemie und Chemie
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Licence (German):License LogoCreative Commons - Namensnennung-Nicht kommerziell - Keine Bearbeitung 4.0