An N-heterocyclic carbene-based pincer system of palladium and its versatile reactivity under oxidizing conditions

NHC-based pincers (NHC = N-heterocyclic carbene) have been broadly employed as supporting platforms, and their palladium complexes have found many synthetic applications. However, previous studies mainly focused on the NHC pincers of palladium featuring an oxidation number of +II. In contrast, oxidation of these well-defined Pd(II) species and the study of their fundamental high-valent Pd chemistry remain largely undeveloped. In addition, from a perspective of Pd^II/Pd^IV catalysis, the reactivity and degradation of NHC pincers in catalytically relevant reactions have not been well understood. In this work, a series of Pd(II) complexes supported by a well-known NHC^Aryl^NHC pincer platform have been prepared. Their reactivity towards various oxidizing reagents, including halogen surrogates, electrophilic fluorine reagents, and alkyl/aryl halides, has been examined. In some cases, ambient-characterizable high-valent Pd NHCs, which have been scarcely reported, were obtained. The carbenes incorporated into the pincer framework proved to be effective spectator donors. In contrast, the central aryl moiety exhibits versatile reactivity and collapse pathways, allowing it to function either as a spectator or a non-innocent actor.