Employing Aryl-Linked Bis-mesoionic Carbenes as a Pincer-Type Platform to Access Ambient-Stable Palladium(IV)...

The study of palladium(IV) species has great implications for Pd^II /Pd^IV -mediated catalysis. However, most of the Pd^IV complexes rapidly decompose under ambient conditions, which makes the isolation, characterization and further reactivity study very challenging. The reported ancillary ligand platforms to stabilize Pd^IV species are dominated by chelating N-donors such as bipyridines. In this work, we present two Pd^IV complexes with scarcely used C-donors as the supporting platform. The anionic aryl donor and MIC (MIC=mesoionic carbene) are combined in a [CC'C]-type pincer framework to access a series of ambient-stable Pd^IV tris(halido) complexes. Their synthesis, solid-state structures, stability, and reactivity are presented. To the best of our knowledge, the work presented herein reports the first isolated Pd^IV -MIC as well as the first Pd^IV carbene-based aryl pincer.