[Pd(NHC)(μ-Cl)Cl]

ConspectusPalladium-catalyzed cross-coupling reactions owing to their high specificity and superb chemoselectivity represent a powerful tool for the rapid construction of C-C and C-X bonds across various areas of chemical research, including pharmaceutical development, polymer and agrochemical industries, bioactive natural products, and advanced functional materials, rendering them indispensable for modern synthetic chemists. The major driving force for the advances in this critical field is the design of increasingly more reactive and more selective ligands and precatalysts that aim not only to address challenging cross-coupling processes but also to achieve optimal reactivity, selectivity, and functional group compatibility under mild, user-friendly, operationally simple, and broadly applicable conditions. In this context, Pd(II)-N-heterocyclic carbene complexes (NHC = N-heterocyclic carbene) have garnered prevalent attention among practitioners of organic synthesis due to their unique electronic and steric characteristics that are unmatched among other ligands. In particular, the superior σ-donating ability of NHC ligands in conjunction with conformational flexibility as well as the ease of steric and electronic modification and high stability to air and moisture enable highly effective fundamental elementary steps in catalytic cycles and facile formation of well-defined complexes.The key factor in the design of well-defined, air- and moisture-stable Pd(II) precatalysts involves the incorporation of supporting ligands, which are essential for ensuring the stability of Pd(II)-NHC complexes and facile activation of Pd(II)-NHC precatalysts to catalytically active monoligated Pd(0)-NHC species under the reaction conditions. Notably, [Pd(NHC)(μ-Cl)Cl]