Anionic N-Heterocyclic Carbene Ligands from Mesoionic Imidazolium Precursors: Remote Backbone Arylimino Substitution Directs Carbene Coordination

Authors

  • Prof. Dr. Andreas A. Danopoulos,

    Corresponding author
    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex (France)
    • Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex (France)
    Search for more papers by this author
  • Dr. Kirill Yu. Monakhov,

    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex (France)
    Search for more papers by this author
  • Prof. Dr. Pierre Braunstein

    Corresponding author
    1. Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex (France)
    • Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg Cedex (France)
    Search for more papers by this author

Abstract

original image

Versatile precursor to metal complexes: The lithiated N-heterocyclic carbene derivative [Li(imino–imidide)(tmeda)] (imino–imidide=4-(2,6-diisopropylphenylimino)imidazol-2-ylidenide), obtained by deprotonation and lithiation of a mesoionic 4-aryliminoimidazolium, serves as a versatile precursor to metal complexes with the anionic 4-aryliminoimidazolide by salt metathesis. DFT calculations demonstrate that tuneable electronic and steric factors of the substituent at the Nexo imino function of the heterocycle dictate the preferred site of the metallation (CNHC vs. Nexo).

Ancillary