A kinetic analysis of two oxidizing systems, MoO2(acac)2-H2O2 in EtOH and MoO5HMPT in DCE in the epoxidation of two alkenes, 1-methyl-cyclohexene and cyclohexene, and an allylic alcohol, geraniol, has been carried out. The oxidation has been studied both in the absence and in the presence of HMPT (hexamethylphosphorotriamide), a strong complexing agent of molybdenum(VI) peroxo complexes. The kinetic behaviour observed and, in particular, the effect on the oxidation rates of added HMPT, leads to the conclusion that the oxidative process is carried out in solution by different Mo(VI)-peroxo complexes, carrying solvent molecules, substrate and HMPT in the coordination sphere, all acting as electrophilic oxidants toward an uncomplexed olefin molecule. © 1983.
Metal Catalysis in Oxidation by Peroxides. Part 18. On the mechanism of Electrophilic Olefin Epoxidation by Molybdenum (VI) Peroxocomplex
BORTOLINI, Olga;
1983
Abstract
A kinetic analysis of two oxidizing systems, MoO2(acac)2-H2O2 in EtOH and MoO5HMPT in DCE in the epoxidation of two alkenes, 1-methyl-cyclohexene and cyclohexene, and an allylic alcohol, geraniol, has been carried out. The oxidation has been studied both in the absence and in the presence of HMPT (hexamethylphosphorotriamide), a strong complexing agent of molybdenum(VI) peroxo complexes. The kinetic behaviour observed and, in particular, the effect on the oxidation rates of added HMPT, leads to the conclusion that the oxidative process is carried out in solution by different Mo(VI)-peroxo complexes, carrying solvent molecules, substrate and HMPT in the coordination sphere, all acting as electrophilic oxidants toward an uncomplexed olefin molecule. © 1983.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
