Medium effects in weakly coupled electron-transfer processes. Calculation of inner-sphere reorganizational energies at zero ionic strength

Nita Lewis, Yaw S. Obeng, William L. Purcell

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Abstract

The solvent dependence of the intervalence transition (IT) band of the very weakly coupled binuclear (2,8-dithiadispiro-[3.1.3.1]decane)decaamminediruthenium(II,III) hexafluorophosphate was studied. No correlation could be discerned with any solvent parameter. A dependence of the optical band of the ruthenium binuclear complex, Eop, on the ionic strength of the medium was observed, with some solvents showing stronger effects than others. When ionic strength studies were performed and the extrapolated values at zero ionic strength were employed, a correlation of Eop0 with 1/Dop - 1/Ds was observed. The calculated inner-sphere reorganizational energy, λi, was 25 kcal/mol. The calculated slope of the plot of Eop0 against 1/Dop - 1/Ds was 20.7 whereas the measured value was only 2.02. These results indicate that the dielectric continuum model is not appropriate for theories used in analyzing IT bands of very weakly coupled mixed-valence complexes.

Original languageEnglish
Pages (from-to)3796-3799
Number of pages4
JournalInorganic Chemistry
Volume28
Issue number20
StatePublished - Dec 1 1989

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ASJC Scopus subject areas

  • Inorganic Chemistry

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