Protic NHC Iridium Complexes with β-H Reactivity–Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation

Protic NHC iridium complexes, obtained from the corresponding azido-phenylene-isocyanide precursor complexes, were investigated for ligand-based reactivity. Under redox-neutral conditions, acetonitrile inserts into the N-H bonds to provide kappa(2)-NHC-imidoyl ligand-based complexes, while under reductive conditions the complex also expels one N-H proton to provide the corresponding deprotonated analogues. Using zinc as a reductor activates the NHC-iridium complex to form an asymmetric bimetallic iridium hydrido complex, in which two anionic N-deprotonated NHCs bridge the bimetallic core. X-ray crystal structures are reported for the azido-phenylene-isocyanide precursor complex, the protic NHC complex, and the asymmetric bimetallic iridium hydride complex. Density functional computations and a QTAIM analysis of the bimetallic iridium hydrido complex are provided.