Methimazole complexes of platinum(II): Synthesis, characterization and redox behavior

A variety of platinum(II) complexes of methimazole (2-mercapto-1-methylimidazole; HImS=neutral form and ImS=thiolate form), coordinated in both thione and thiolate forms, have been isolated by reacting methimazole with [PtCl(terpy)]Cl (terpy=2,2′:6′,2″ terpyridine), [PtCl2(bipy)] (bipy=bipyridine), [PtCl2(o-phen)] (o-phen=o-phenanthroline), [PtCl2(CH3CN)2] and [PtCl2(COD)] (COD=1,5-cyclooctadiene). These complexes were characterized by electronic absorption, IR and NMR (1H, 13C, 195Pt) spectroscopies. Molecular structure of [Pt(bipy)(HImS)2]Cl2·3H2O (3a·3H2O) has been established by single crystal X-ray crystallography. Platinum thiolate complex, [Pt(ImS)2(HImS)2] (5), could be obtained by treatment of [Pt(HImS)4]Cl2 with sodium methoxide in methanol. The solution of 5 in organic solvents yielded bi- and tri-nuclear platinum complexes. The effect of diimine ligands on oxidation of methimazole moiety in the complexes has been studied by electrochemical oxidation and pulse radiolytic oxidation employing specific one-electron oxidant, N3 radical.