Palladium(II) thiocarboxamide complexes: synthesis, characterisation and application to catalytic Suzuki coupling reactions

A simple route to synthesise palladium(II) complexes from the reaction of N-substituted pyridine-2-thiocarboxamide ligands and PdCl2(PPh3)(2) has been developed. The new complexes are very soluble in common solvents and have been fully characterised (elemental analysis, FT-IR, H-1, P-31, C-13-NMR), including an X-ray diffraction analysis. The molecular structures of all the complexes were determined and reveal the presence of square planar geometry around Pd with little distortion. The complexes were tested in the Suzuki coupling of electronically deactivated aryl and heteroaryl bromides and were found to have much greater activity, without using any promoting additives or phase transfer agent under aerobic conditions. Higher reaction rates are obtained by varying R substituents on the aromatic ring of pyridine-2-thiocarboxamide. The effect of other variables on the cross-coupling reaction, such as temperature, solvent and base, is also reported.