Synthesis and Isolation of an Anionic Bis(dipyrido-annulated) N‑Heterocyclic Carbene CCC-Pincer Iridium(III) Complex by Facile C–H Bond Activation

Meridional tridentate N-heterocyclic carbene (NHC)-based pincer ligands contribute to a substantial growth in modern organometallic chemistry in both homogeneous catalysis and luminescence materials. Among all NHC-based pincer ligands, the dianionic LX2-type CCC-pincer ones constitute the smallest subcategory owing to their limited ligand frameworks suitable for complexation. This work reports a one-pot, high-yield synthesis of a homoleptic anionic all-carbon bis-pincer iridium­(III) complex (4) directly from a bis­(aryl)-substituted dipyrido-annulated (dpaAr2) imidazolium salt and [Ir­(COD)­Cl]2 via a cascade of deprotonation/C–H activation processes. Both experimental complexation chemistry and computational mechanistic investigation suggest that the large bite angle and π-rich character of the dpaAr2 NHC are responsible for its facile complexation as a dianionic LX2-type CCC-pincer ligand precursor. The all-carbon ligated iridium­(III) complex (4) bearing a π-conjugated ligand scaffold showed remarkably low oxidation potentials, which allows future investigations in its redox chemistry and photophysical properties.