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

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Rong , M K , Chirila , A , Franciolus , D , Lutz , M , Nieger , M , Ehlers , A W , Slootweg , J C & Lammertsma , K 2019 , ' Protic NHC Iridium Complexes with beta-H Reactivity-Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation ' , Organometallics , vol. 38 , no. 23 , pp. 4543-4553 . https://doi.org/10.1021/acs.organomet.9b00584

Title: Protic NHC Iridium Complexes with beta-H Reactivity-Synthesis, Acetonitrile Insertion, and Oxidative Self-Activation
Author: Rong, Mark K.; Chirila, Andrei; Franciolus, David; Lutz, Martin; Nieger, Martin; Ehlers, Andreas W.; Slootweg, J. Chris; Lammertsma, Koop
Contributor: University of Helsinki, Department of Chemistry
Date: 2019-12-09
Language: eng
Number of pages: 11
Belongs to series: Organometallics
ISSN: 0276-7333
URI: http://hdl.handle.net/10138/309063
Abstract: 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.
Subject: N-HETEROCYCLIC CARBENE
CATALYTIC INTRAMOLECULAR HYDROAMINATION
CP-ASTERISK-IR
TEMPLATE SYNTHESIS
BOND ACTIVATION
PENTAMETHYLCYCLOPENTADIENYL-RHODIUM
DEPROTONATION REACTIONS
TRANSFER HYDROGENATION
METAL-COMPLEXES
LIGAND
116 Chemical sciences
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