title: Mechanism of selective oxidation of organic sulfides with Oxo(salen)chromium(V) complexes
abstract: The selective oxidation of organic sulfides to sulfoxides by oxo(salen)chromium(V) complexes in acetonitrile is overall second-order, first-order each in the oxidant and the substrate. The rate constant, k(2), values of several para-substituted phenyl methyl sulfides correlate linearly with Hammett sigma constants and the rho values are in the range of -1.3 to -2.7 with different substituted oxo(salen)chromium(V) complexes. The reactivity of different alkyl sulfides is in accordance with Taft's steric substituent constant, E(S). A mechanism involving direct oxygen atom transfer from the oxidant to the substrate rather than electron transfer is envisaged. Correlation analyses show the presence of an inverse relationship between reactivity and selectivity in the reaction of various sulfides with a given oxo(salen)chromium(V) complex and vice versa. Mathematical treatment of the results shows that this redox system falls under strong reactivity-selectivity principle (RSP).
authors.affiliation: Department of Materials Science and School of Chemistry, Madurai Kamaraj University, Madurai - 625 021, India, and Department of Chemistry, Manonmaniam Sundaranar University, Tirunelveli - 627 012, India.
authors.initials: R
authors.lastname: Sevvel
authors.initials: S
authors.lastname: Rajagopal
authors.initials: C
authors.lastname: Srinivasan
authors.initials: NI
authors.lastname: Alhaji
authors.initials: A
authors.lastname: Chellamani