Iodonium Salts of Complex Anions. I. The Self-Phenylation of Diphenyliodonium Salts of Bis(dithiooxalato)palladate(II) and -platinate(II)

The diphenyliodonium salts of the dithiooxalates of palladium(II) and platinum(II), ((C6H5)(2)I)(2)[M(S2C2O2)(2)], were isolated in a study of the phenylating effect of this cation on complex anions. This new ligand reaction was studied in both the solid state and in solution. At 150 in the solid state the products are the polymeric thiophenolates of palladium(II) and platinum(II), palladium also undergoing reduction to the metal to a considerable extent. These mercaptides were found to be soluble in molten triphenylphosphine and were briefly characterized in this solvent. In pyridine solution (pyH)(2)[Pd-S2C2O2)(2)(S2C2O2)(2)) and 2-, 3-, and 4-phenylpyridines were the principal products while the platinum complex gave (Pt(S2C2O2)(PY)-1py(2) and (pyH)(Pt(S2C2O2)(S2C2O2CH6)(py)(2)]. A radical mechanism is proposed for the reactions on the basis of the isolated products.