Sulfide and Sulfoxide Oxidations by Mono- and Diperoxo Complexes of Molybdenum. A Density Functional Study

The molecular mechanism for the oxidation of sulfides to sulfoxides and subsequent oxidation to
sulfones by diperoxo, MoO(O2)2(OPH3) (I), and monoperoxo, MoO2(O2)(OPH3) (II), complexes of
molybdenum was studied using density functional calculations at the b3lyp level and the transition
state theory. Complexes I and II were both found to be active species. Sulfide oxidation by I or II
shows similar activation free energy values of 18.5 and 20.9 kcal/mol, respectively, whereas
sulfoxides are oxidized by I (ΔG⧧ = 20.6 kcal/mol) rather than by II (ΔG⧧ = 30.3 kcal/mol). Calculated
kinetic and thermodynamic parameters account for the spontaneous overoxidation of sulfides to
sulfones as has been experimentally observed. The charge decomposition analysis (CDA) of the
calculated transition structures of sulfide and sulfoxide oxidations revealed that I and II are stronger
electrophilic oxidants toward sulfides than they are toward sulfoxides.