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

作者：CHELLAMANI A^*; ALHAJI NI; RAJAGOPAL S; SEVVEL R; SRINIVASAN C

来源：Tetrahedron, 1995, 51(46): 12677-12698.

DOI：10.1016/0040-4020(95)00825-S

The kinetics of oxygen atom transfer from several cationic oxo(salen)manganese(V) [salen = N,N'-ethylenebis(salicylidineaminato)] complexes to organic sulphides have been studied spectrophotometrically in acetonitrile at 25 degrees C. The reaction follows an overall second-order kinetics, first-order each in sulphide and oxomanganese(V) complex. Electronic-substrate and electronic-oxidant effect studies reveal that the single electron transfer from sulphide to the oxo complex is the rate-controlling step. The redox potentials of the couple Mn-V/Mn-IV have been estimated by applying Marcus theory to the experimentally observed rate constants.

• 出版日期1995-11-13