Cyclopalladation of N,N,N',N'-tetramethylisophthalthioamide

N,N,N',N'-Tetramethylisophthalthioamide (Hmpt) was cyclopalladated with PdCl2 in hot dimethylsulphoxide to give [PdCl(mpt)]. The structure was determined by X-ray analysis. The thioamide is metallated at C(2) to act as an S-C-S tridentate anionic ligand. There is appreciable steric repulsion between the benzene ring H(4, 6) and the dimethylamino groups. The hydrogens and the methyl groups mutually deviate from the coordination plane in opposite directions. The stability of the fused 5,5-membered chelate ring formed by the S-C-S ligand seems to overcome the steric hindrance. Derivatives were prepared by replacement of the chloride ion with iodide, diethyldithiocarbamate, 4-tert-butylpyridine, or tri-n-butylphosphine, and characterized spectroscopically. The S-C-S-fused chelate ring was maintained in these derivatives.