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corresponding to the difference of formal redox potentials of
the fullerene and the 1,2-dihaloethane largely contributes to the
activation energy of reduction of 1,2-dihaloethanes by the
fullerene anions. Noticeably, the larger fullerenes are more stable
than C60 with respect to the alkyl adduct formation. That is, no
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anions of larger fullerenes are better catalysts for electrode-
assisted chemical reactions in terms of the overpotential and
catalyst stability, although the corresponding electrocatalytic rate
constants are much smaller than those for the C60 anions.
In summary, the anions of larger fullerenes, C76, C78, and
C84 electrocatalytically reduce 1,2-dihaloethanes. The dianions
of C76 and C78, as well as trianions of C76, C78, and C84,
electrochemically generated in 0.1 M (TBA)PF6, in benzonitrile,
catalyze dehalogenation of 1,2-dihaloethanes. The second-order
rate constant for the electrocatalytic dehalogenation of 1,2-
dihaloethanes by the fullerene anions, determined by the RDE
voltammetry under pseudo-first-order conditions, increase in the
order Cl < Br < I for the investigated 1,2-dihaloethanes and in
the order C84 < C78 < C76 < C70 < C60 for each 1,2-dihalo-
ethane. No chemical reaction between the anions of larger
fullerenes and 1,2-dihaloethanes resulting in formation of alkyl
adducts of fullerenes is observed. Because of the high stability
with respect to the adduct formation and more positive E1/2
values of the electrocatalyses, the larger fullerenes may be more
useful than C60 as catalysts, even though their corresponding
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Acknowledgment. We thank BG Products, Wichita, for
rendering its GC-MS instrumentation available for the present
investigations. Financial support of the US-Polish Maria Sklo-
dowska-Curie Joint Fund II, through Grant PAN/NSF-96-275
to W.K. and F.D., as well as of the donors of the Petroleum
Research Fund, administered by the American Chemical Society,
is gratefully acknowledged.
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