Intramolecular long-distance electron transfer in radical anions. The effects of free energy and solvent on the reaction rates

  • Miller J
  • Calcaterra L
  • Closs G
  • 147


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Biphenylylandrostanes I (R = 2-naphthyl, 9-phenanthrenyl, 3-pyrenyl), II, III, and IV (R1 = R2 = H, Cl; R1 = H, R2 = Cl) with various electron acceptors at C-3 were prepd. The intramol. rates of electron transfer (ET) from the neg. ions with the charge located on the biphenyl moiety to the acceptor was measured in 2-methyltetrahydrofuran by pulse radiolysis techniques. There is a strong dependence on the exothermicity of the ET reaction displaying a max., the position of which is detd. by the reorganization energy. Consequently, reactions run in isooctane were very much faster at low exothermicity but slowed down very much at -Delta G > 1.5 eV. on SciFinder (R)

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  • J. R. Miller

  • L. T. Calcaterra

  • G. L. Closs

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