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

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posted on 2019-11-19, 17:06 authored by Mark K. Rong, Andrei Chirila, David Franciolus, Martin Lutz, Martin Nieger, Andreas W. Ehlers, J. Chris Slootweg, Koop Lammertsma
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 κ2-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.

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