Voltammetry of the complexes of the platinum metals with organic sulphides in acetonitrile

The electrochemical behaviour of palladium(II), ruthenium(III), rhodium(III), osmium(IV), iridium(IV) and platinum(IV) complexes with a number of sulphides was investigated at a glassy carbon electrode in acetonitrile. Complexes of Ru(III), Os(IV) and Ir(IV) have been found to undergo a reversible one-electron transfer yielding Ru(II), Os(III) and Ir(III) complexes. Electroreduction of the Ru(II) and Ir(III) compounds is of the EC type and is accompanied by the rearrangement of the complex coordination sphere. Compounds of Pd(II), Rh(III) and Pt(IV) are reduced with the transfer of 2 electrons in the first stage. The electrode process differs from a reversible one and is complicated by the dissociation reaction of the ligands. The influence of the nature of the donor atoms on the oxidation potentials of the complexes is considered. © 1988