Mesoionic and Related Less Heteroatom-Stabilized N-Heterocyclic Carbene Complexes: Synthesis, Catalysis, and Other Applications

Mesoionic carbenes are a subclass of the family of N-heterocyclic carbenes that generally feature less heteroatom stabilization of the carbenic carbon and hence impart specific donor properties and reactivity schemes when coordinated to a transition metal. Therefore, mesoionic carbenes and their complexes have attracted considerable attention both from a fundamental point of view as well as for application in catalysis and beyond. As a follow-up of an earlier Chemical Reviews overview from 2009, the organometallic chemistry of N-heterocyclic carbenes with reduced heteroatom stabilization is compiled for the 2008 2017 period, including specifically the chemistry of complexes containing 1,2,3-triazolylidenes, 4-imidazolylidenes, and related 5-membered N-heterocyclic carbenes with reduced heteratom stabilization such as (is)oxazolylidenes, pyrrazolylidenes, and thiazolylidenes, as well as pyridylidenes as 6-membered N-heterocyclic carbenes with reduced heteroatom stabilization. For each ligand subclass, metalation strategies, electronic and steric properties, and applications, in particular, in metal-mediated catalysis, are compiled. Mesoionic carbenes demonstrate particularly high activity in (water) oxidation, hydrogen transfer reactions, and cyclization reactions. Unique features of these ligands are identified such as their dipolar structure, their specific donor properties, as well as stability aspects of the ligand and the complexes, which provides opportunities for further research.