Outer-sphere coordination effects on the redox behaviour of the Fe(CN)63−/Fe(CN)64− couple in non-aqueous solvents |
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Authors: | G. Gritzner K. Danksagmüller V. Gutmann |
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Affiliation: | Institute of Inorganic Chemistry, Technical University, Getreidemarkt 9, A-1060 Vienna (Austria) |
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Abstract: | The polarographic behaviour of tetra-n-butylammonium hexacyanoferrate(II) has been studied in N-methylpyrrolidinone, N,N-dimethylformamide, acetonitrile, dimethylsulphoxide, N,N-dimethylthioformamide, 1,2-dichloroethane, propanediolcarbonate, nitromethane, ethanol, methanol and acetic acid using tetrabutylammonium perchlorate as supporting electrolyte. A polarographically reversible electrode process was found in all solvents but acetic acid. The large shift in half-wave potentials (vs. bisbiphenylchromium(I) as a reference ion) is interpreted on the basis of donor-acceptor interactions between the hexacyanoferrate ions and solvent molecules and also between the hexacyanoferrate ions and cations of the supporting electrolyte. The considerable difference in half-wave potentials between tetraethylammonium and tetrabutylammonium perchlorate is discussed within the framework of this concept. |
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