Anionic N‐Heterocyclic Carbene Ligands from Mesoionic Imidazolium Precursors: Remote Backbone Arylimino Substitution Directs Carbene Coordination. Issue 2 (23rd December 2012) - Danopoulos, Andreas A.
Abstract 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).