title: Epoxidation of alkenes with hydrogen peroxide catalyzed by selenium-containing dinuclear peroxotungstate and kinetic, spectroscopic, and theoretical investigation of the mechanism.
abstract: The dinuclear peroxotungstate with a SeO(4)(2-) ligand, (TBA)(2)[SeO(4){WO(O(2))(2)}(2)] (I; TBA = [(n-C(4)H(9))(4)N](+)), could act as an efficient homogeneous catalyst for the selective oxidation of various kinds of organic substances such as olefins, alcohols, and amines with H(2)O(2) as the sole oxidant. The turnover frequency (TOF) was as high as 210 h(-1) for the epoxidation of cyclohexene catalyzed by I with H(2)O(2). The catalyst was easily recovered and reused with maintenance of the catalytic performance. The SeO(4)(2-) ligand in I played an important role in controlling the Lewis acidity of the peroxotungstates, which significantly affects their electrophilic oxygen-transfer reactivity. Several kinetic and spectroscopic results showed that the present catalytic epoxidation included the following two steps: (i) formation of the subsequent peroxo species [SeW(m)O(n)](o-) (II; m = 1 and 2) by the reaction of I with an olefin and (ii) regeneration of I by the reaction of II with H(2)O(2). Compound I was the dominant species under steady-state turnover conditions. The reaction rate for the catalytic epoxidation showed a first-order dependence on the concentrations of olefin and I and a zero-order dependence on the concentration of H(2)O(2). The rate of the stoichiometric epoxidation with I agreed well with that of the catalytic epoxidation with H(2)O(2) by I. All of these kinetic and spectroscopic results indicate that oxygen transfer from I to the C=C double bond is the rate-determining step. The computational studies support that the oxygen-transfer step is the rate-determining step.
authors.affiliation: Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
authors.forename: Keigo
authors.initials: K
authors.lastname: Kamata
authors.forename: Ryo
authors.initials: R
authors.lastname: Ishimoto
authors.forename: Tomohisa
authors.initials: T
authors.lastname: Hirano
authors.forename: Shinjiro
authors.initials: S
authors.lastname: Kuzuya
authors.forename: Kazuhiro
authors.initials: K
authors.lastname: Uehara
authors.forename: Noritaka
authors.initials: N
authors.lastname: Mizuno