Sulfur-assisted chloride and triphenylphosphine dissociation of palladium(II) complex [Pd(PPh3)2(η1-SCNMe2)(Cl)]. X-ray structures of [Pd(PPh3)2(η1-SCNMe2)(Cl)], [Pd(PPh3)(Cl)]2(μ,η2-SCNMe2)2, and [Pd(PPh3)2(η2-SCNMe2)][PF6]

Treatment of Pd(PPh3)4 with Me2NC(S)Cl in dichloromethane at −20 °C produces the complex [Pd(PPh3)2(η1-SCNMe2)(Cl)], 2. Variable temperature 1H and 31P{H} NMR experiments of complex 2 shows the dissociation of either the chloride or the triphenylphosphine ligand to form complex [Pd(PPh3)2(η2-SCNMe2)][Cl], 3 or the dipalladium complex [Pd(PPh3)Cl]2(μ,η2-SCNMe2)2, 4. The reaction of complex 2 with NaPF6 affords complex [Pd(PPh3)2(η2-SCNMe2)][PF6], 5. Complexes 2, 4, and 5 are characterized by X-ray diffraction analyses.