1,3‐Imidazole‐Based Mesoionic Carbenes and Anionic Dicarbenes: Pushing the Limit of Classical N‐Heterocyclic Carbenes

Abstract Classical N‐heterocyclic carbenes (NHCs) featuring the carbene center at the C2‐position of 1,3‐imidazole framework (i.e. C2‐carbenes) are well acknowledged as very versatile neutral ligands in molecular as well as in materials sciences. The efficiency and success of NHCs in diverse areas is essentially attributed to their persuasive stereoelectronics, in particular the potent σ‐donor property. The NHCs with the carbene center at the unusual C4 (or C5) position, the so‐called abnormal NHCs (aNHCs) or mesoionic carbenes (iMICs), are however superior σ‐donors than C2‐carbenes. Hence, iMICs have substantial potential in sustainable synthesis and catalysis. The main obstacle in this direction is rather demanding synthetic accessibility of iMICs. The aim of this review article is to highlight recent advances, particularly by the author's research group, in accessing stable iMICs, quantifying their properties, and exploring their applications in synthesis and catalysis. In addition, the synthetic viability and use of vicinal C4,C5‐anionic dicarbenes (ADCs), also based on an 1,3‐imidazole framework, are presented. As will be apparent on following pages, iMICs and ADCs hold potentials in pushing the limit of classical NHCs by enabling access to conceptually new main‐group heterocycles, radicals, molecular catalysts, ligands sets, and more.