Get access

CO2 and Formate Complexes of Phosphine/Borane Frustrated Lewis Pairs

Authors

  • Ilona Peuser,

    1. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6 (Canada)
    2. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    Search for more papers by this author
  • Rebecca C. Neu,

    1. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6 (Canada)
    2. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    Search for more papers by this author
  • Xiaoxi Zhao,

    1. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6 (Canada)
    Search for more papers by this author
  • Dr. Matthias Ulrich,

    1. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6 (Canada)
    Search for more papers by this author
  • Birgitta Schirmer,

    1. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    Search for more papers by this author
  • Jens A. Tannert,

    1. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    Search for more papers by this author
  • Dr. Gerald Kehr,

    1. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    Search for more papers by this author
  • Dr. Roland Fröhlich,

    1. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    Search for more papers by this author
  • Prof. Dr. Stefan Grimme,

    Corresponding author
    1. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    • Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    Search for more papers by this author
  • Prof. Dr. Gerhard Erker,

    Corresponding author
    1. Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    • Organisch-Chemisches Institut der Universität Münster, Corrensstrasse 40, 48149 Münster (Germany)
    Search for more papers by this author
  • Prof. Dr. Douglas W. Stephan

    Corresponding author
    1. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6 (Canada)
    • Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON, M5S 3H6 (Canada)
    Search for more papers by this author

Abstract

The reaction of a solution of B(C6F4H)3 and either iPr3P or tBu3P with CO2 afforded the species R3P(CO2)B(C6F4H)3 (R=iPr (1), tBu (2)). In a similar fashion the boranes, RB(C6F5)2 (R=hexyl, cyclohexyl (Cy), norbornyl), ClB(C6F5)2, or PhB(C6F5)2 were combined with tBu3P and CO2 to give the species tBu3P(CO2)BR(C6F5)2 (R=hexyl (3), Cy (4), norbornyl (5), Cl (6), Ph (7)). Similarly, the compounds [tBu3PH][RBH(C6F5)2] (R=hexyl (8), Cy (9), norbornyl (10)) were prepared by reaction of the precursor frustrated Lewis pair (FLP) with H2. Subsequent reactions of 9 and 10 with CO2 afforded the species [((C6F5)2BR)2(μ-HCO2)][tBu3PH] (R=Cy (11), norbornyl (12)). In related chemistry, combinations of the boranes RB(C6F5)2 (R=hexyl, Cy, norbornyl) with tBu3P treated with an equivalent of formic acid gave [(C6F5)2BR(HCO2)][tBu3PH] (R=hexyl (13), Cy (14), norbornyl (15)). Subsequent addition of an additional equivalent of borane provides a second synthetic route to 11 and 12. Crystallographic studies of compounds 26 and 814 are reported and discussed. Further understanding of the FLP complexation and activation of CO2 is provided by computational studies.

Ancillary