MECHANISM OF OXIDATION OF ORGANIC SULFIDES BY OXO(SALEN)MANGANESE(V) COMPLEXES

The kinetics of oxygen atom transfer from several cationic oxo(salen)m anganese(V) [salen = N,N'-ethylenebis(salicylidineaminato)] complexes to organic sulphides have been studied spectrophotometrically in aceto nitrile at 25 degrees C. The reaction follows an overall second-order kinetics, first-order each in sulphide and oxomanganese(V) complex. El ectronic-substrate and electronic-oxidant effect studies reveal that t he single electron transfer from sulphide to the oxo complex is the ra te-controlling step. The redox potentials of the couple Mn-V/Mn-IV hav e been estimated by applying Marcus theory to the experimentally obser ved rate constants.