The electroreductions of Buckminsterfullerene (c60) in aprotic solvents were examined as a function of solvent, supporting electrolyte, and temperature. Altogether, 11 different solvents and 17 different supporting electrolytes were utilized in measurements made between 223 and 348 K. The cations of the supporting electrolytes were Li' and Na+ as well as quaternary ammonium and quaternary phosphonium cations. The anions of the supporting electrolytes were C104-, BF4-, PF6-, and Br-. Cyclic voltammograms, rotating disk electrode voltammograms, and controlled potential coulometry revealed up to five reversible one-electron reductions. A qualitative approach is used to elucidate the effects of solvent, supporting electrolyte, and temperature on the half-wave potentials, E l / z , of the reductions of c 6 0 . E l l 2 for the first reduction correlates well with the Gutmann donor number of the solvent with a positive slope, but it also shows a linear correlation with the Gutmann acceptor number of the solvent with a negatiue slope. In contrast, the third reduction E1/2 correlates fairly with the Gutmann acceptor number with a positive slope. The first three reductions also correlate with the normalized Dimroth-Reichardt solvent parameter. The inorganic anions of the supporting electrolytes do not significantly affect the half-wave potentials, but these values vary substantially with the type and size of the supporting electrolyte cations. The relative magnitudes of the solvent and supporting electrolyte effects on E l I z differ for each redox process of Cdo, and values of shift over a range of 280-600 mV for a given redox couple. The shifts in reduction potentials were rationalized in terms of the following: (i) charge density on the fulleride anions, (ii) solvophobic effects involving Cso (aggregation), (iii) solvophobic type interactions involving Cm anions and the larger cations of the supporting electrolytes in polar solvents, (iv) ion pairing of Cdo anions with smaller cations in nonpolar solvents, and (v) the specific acceptor or donor properties of the solvents. The reversible half-wave potentials were also measured as a function of temperature in eight different solvent/supporting electrolyte systems, and the measured values of AElI2/AT were used to calculate the change of entropy associated with each electron-transfer step. The shifts in E l I z with temperature are relatively large and indicate that an unusually large change of entropy accompanies each electroreduction step. Diffusion coefficients, Stokes radii, and apparent solvation numbers of neutral Cdo were also determined in different solvent systems, and these values are discussed with respect to the nature of the solventsolute interaction.

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The legends of the Scheme and Figures have been transposed. The figure labelled as Scheme 1 is in fact Fig. 1 (cyclic voltammograms in PhCN). The figure labelled as Fig. 1 is Fig. 2 (cyclic voltammograms in thf). The figure labelled as Fig. 2 is Fig.

The overall two-electron oxidation and two-electron reduction of (tpp)Eu(facam) is monitored by cyclic voltammetry in severa I solvent/supporti ng electrolyte mixtures.