Fluorescence from Samarium(II) Iodide and Its Electron Transfer Quenching: Dynamics of the Reaction of Benzyl Radicals with Sm(II) |
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Authors: | Skene W. G. Scaiano J. C. Cozens F. L. |
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Affiliation: | Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada. |
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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. |
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