om9b00584_si_002.xyz (35.58 kB)
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 LammertsmaProtic 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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protic NHCN-deprotonated NHCs bridgeNHC-imidoyl ligand-based complexesacetonitrile insertsligand-based reactivitybimetallic coreredox-neutral conditionsazido-phenylene-isocyanide precursor complexesX-ray crystal structuresOxidative Self-Activation Protic NHC iridium complexesbimetallic iridium hydridoreductive conditionsbimetallic iridium hydrideQTAIM analysisProtic NHC Iridium Complexesreductor activatesdeprotonated analoguesazido-phenylene-isocyanide precursorκ 2
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