Rong, Mark K. Chirila, Andrei Franciolus, David Lutz, Martin Nieger, Martin Ehlers, Andreas W. Slootweg, J. Chris Lammertsma, Koop 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 κ<sup>2</sup>-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. protic NHC;N-deprotonated NHCs bridge;NHC-imidoyl ligand-based complexes;acetonitrile inserts;ligand-based reactivity;bimetallic core;redox-neutral conditions;azido-phenylene-isocyanide precursor complexes;X-ray crystal structures;Oxidative Self-Activation Protic NHC iridium complexes;bimetallic iridium hydrido;reductive conditions;bimetallic iridium hydride;QTAIM analysis;Protic NHC Iridium Complexes;reductor activates;deprotonated analogues;azido-phenylene-isocyanide precursor;κ 2 2019-11-19
    https://acs.figshare.com/articles/journal_contribution/Protic_NHC_Iridium_Complexes_with_H_Reactivity_Synthesis_Acetonitrile_Insertion_and_Oxidative_Self-Activation/10354715
10.1021/acs.organomet.9b00584.s001