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Updated: Dec 1, 2025

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Nickel-Catalyzed Intramolecular 1,2-Aryl Migration of Mesoionic Carbenes (iMICs)
Arne Merschel1, Timo Glodde1, Beate Neumann1
1Molecular Inorganic Chemistry and Catalysis, Inorganic and Structural Chemistry, Center for Molecular Materials, Faculty of Chemistry, Universität Bielefeld, Universitätsstrasse 25, 33615, Bielefeld, Germany.
Abstract:
Intramolecular 1,2-Dipp migration of seven mesoionic carbenes (iMICAr ) 2 a-g (iMICAr =ArC{N(Dipp)}2 CHC; Ar=aryl; Dipp=2,6-iPr2 C6 H3 ) under nickel catalysis to give 1,3-imidazoles (IMDAr ) 3 a-g (IMDAr =ArC{N(Dipp)CHC(Dipp)N}) has been reported. The formation of 3 indicates the cleavage of an N-CDipp bond and the subsequent formation of a C-CDipp bond in 2, which is unprecedented in NHC chemistry. The use of 3 in accessing super-iMICs (5) (S-iMIC=ArC{N(Dipp)N(Me)C(Dipp)}C) has been shown with selenium (6), gold (7), and palladium (8) compounds. The quantification of the stereoelectronic properties reveals the superior σ-donor strength of 5 compared to that of classical NHCs. Remarkably, the percentage buried volume of 5 (%Vbur =45) is the largest known amongst thus far reported iMICs. Catalytic studies show a remarkable activity of 5, which is consistent with their auspicious stereoelectronic features.
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