title: Mechanisms of hydrogen-, oxygen-, and electron-transfer reactions of cumylperoxyl radical.
abstract: Rates of hydrogen-transfer reactions from a series of para-substituted N,N-dimethylanilines to cumylperoxyl radical and oxygen-transfer reactions from cumylperoxyl radical to a series of sulfides and phosphines have been determined in propionitrile (EtCN) and pentane at low temperatures by use of ESR. The observed rate constants exhibit first-order and second-order dependence with respect to concentrations of N,N-dimethylanilines. This indicates that the hydrogen- and oxygen-transfer reactions proceed via 1:1 charge-transfer (CT) complexes formed between the substrates and cumylperoxyl radical. The primary kinetic isotope effects are determined by comparing the rates of N,N-dimethylanilines and the corresponding N,N-bis(trideuteriomethyl)anilines. The isotope effect profiles are quite different from those reported for the P-450 model oxidation of the same series of substrates. Rates of electron-transfer reactions from ferrocene derivatives to cumylperoxyl radical have also been determined by use of ESR. The catalytic effects of Sc(OTf)(3) (OTf = triflate) on the electron-transfer reactions are compared with those of Sc(OTf)(3) on the hydrogen- and oxygen-transfer reactions. Such comparison provides strong evidence that the hydrogen- and oxygen- transfer reactions of cumylperoxyl radical proceed via a one-step hydrogen atom and oxygen atom transfer rather than via an electron transfer from substrates to cumylperoxyl radical.
authors.affiliation: Contribution from the Department of Material and Life Science, Graduate School of Engineering, Osaka University, CREST, Japan Science and Technology Corporation (JST), Suita, Osaka 565-0871, Japan. fukuzumi@chem.eng.osaka-u.ac.jp
authors.forename: Shunichi
authors.initials: S
authors.lastname: Fukuzumi
authors.forename: Kanji
authors.initials: K
authors.lastname: Shimoosako
authors.forename: Tomoyoshi
authors.initials: T
authors.lastname: Suenobu
authors.forename: Yoshihito
authors.initials: Y
authors.lastname: Watanabe