title: A non-radical chain mechanism for oxygen atom transfer with a thiorhenium(V) catalyst.
abstract: The compound MeRe(S)(mtp)(PPh3), 2, where mtpH2 is 2-(mercaptomethyl)thiophenol, was used to catalyze the reaction between pyridine N-oxides, PyO, and triphenylphosphine. The rate law is -d[PyO]/dt=kc'[2].[PyO](1/2), with kc' at 25.0 degrees C in benzene=0.68 (4-picoline N-oxide) and 3.5x10(-3) dm(3/2) mol(-1/2) s(-1) (4-NO2-pyridine N-oxide). A chain mechanism with three steady-state thiorhenium species as chain carriers is implicated.
authors.affiliation: Ames Laboratory and the Department of Chemistry, Iowa State University, Ames, Iowa 50011, USA.
authors.forename: Katalin
authors.initials: K
authors.lastname: Osz
authors.forename: James H
authors.initials: JH
authors.lastname: Espenson