Isolation and Characterization of Sulfonium-Ylide-Stabilized Palladium Carbenes

Isolable sulfonium-ylide-stabilized palladium carbene complexes were synthesized through palladium(II)-induced cyclization of 1,2-alkynylarylsulfanes. X-ray crystallographic analysis characterized the maintenance of a palladium +2 oxidation state, with carbene-carbon–palladium bond lengths of 1.95 Å, indicating a partial double-bond character. These endocyclic sulfonium ylide carbenes represent the first characterized and/or isolable examples of this ligand class; such groups were previously proposed as reaction intermediates during cyclization–carbonylation reactions. A variety of palladium(II) complexes bearing sulfonium-ylide carbene ligands, with differing substituents, were synthesized, and the structure and stability of these complexes in solution were analyzed by 1 H and 13 C NMR spectroscopy, revealing reversibility and a stability dependence on substituents. The chirality of the sulfur heteroatom and the overall properties these ligands provide a potential electronic and steric alternative to existing carbene ligands, which could facilitate the future development of complementary metal-based reactivity.