Mechanistic Insights in the Exchange of Arylthiolate Groups in Aryl(arylthiolato)palladium Complexes Supported by a Dippe Ligand

Carbon–sulfur activation of phenyl p-tolyl sulfide by a mixture of [Pd­(dippe)­(μ-H)]2 (1a) and dinuclear Pd(0), [(μ-dippe)­Pd]2 (1b) (dippe = 1,2-bis­(diisopropylphosphino)­ethane), to yield four carbon–sulfur activation products, (dippe)­Pd­(p-tolyl)­(SPh) (3a), (dippe)­Pd­(Ph)­(S-p-tolyl) (3b), (dippe)­Pd­(SPh)­(Ph)­(3c), and (dippe)­Pd­(p-tolyl)­(S-p-tolyl) (3d), was investigated. The carbon–sulfur complexes 3a–3d were completely characterized by 1H, 31P, and 13C NMR spectroscopy, elemental analysis, and X-ray diffraction. Exchange interactions between arylthiolate groups in (dippe)­Pd­(Ar)­(SAr′) (3a–3d) were investigated, leading to understanding the mechanism of interconversions among the complexes.