title: Fluorescence from Samarium(II) Iodide and Its Electron Transfer Quenching: Dynamics of the Reaction of Benzyl Radicals with Sm(II).
abstract: The luminescence from SmI(2) in THF can be readily quenched by a variety of electron acceptors. In the case of organohalides, the reaction is quite fast; for example, for dichloromethane the rate constant is 2.7 x 10(8) M(-)(1) s(-)(1). Electron transfer leads to halide loss and formation of the carbon-centered radical. In the case of benzyl chloride, the benzyl radicals produced can be readily detected using laser flash photolysis techniques. This electron-transfer reaction has been used as a source of benzyl radicals in order to determine the rate constant for their reaction with SmI(2); the value obtained is (5.3 +/- 1.4) x 10(7) M(-)(1) s(-)(1) in THF at room temperature. The effect of HMPA on the spectroscopic properties of SmI(2) has also been examined.
authors.affiliation: Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
authors.forename: W. G.
authors.initials: WG
authors.lastname: Skene
authors.forename: J. C.
authors.initials: JC
authors.lastname: Scaiano
authors.forename: F. L.
authors.initials: FL
authors.lastname: Cozens