ELECTROCATALYTIC REDUCTION OF ALPHA,OMEGA-DIIODOALKANES I(CH2)(M)I (M=1-8) BY C-60(N-) (N=1-3) ANIONS IN SOLUTION AND AT THE C-60 FILM-MODIFIED ELECTRODES
F. Dsouza et al., ELECTROCATALYTIC REDUCTION OF ALPHA,OMEGA-DIIODOALKANES I(CH2)(M)I (M=1-8) BY C-60(N-) (N=1-3) ANIONS IN SOLUTION AND AT THE C-60 FILM-MODIFIED ELECTRODES, JOURNAL OF PHYSICAL CHEMISTRY B, 102(1), 1998, pp. 212-217
Electroreduction of a homologous series of alpha,omega-diiodoalkanes I
(CH2)(m)I (m=1-8) is shown to be catalyzed by C-60(n-) anions (n = 2,
3) both in solution and at a C-60 film-coated electrode. Solution elec
trocatalysis occurred for the anions of n = 2 and 3 in 0.1 M (TBA)PF6
in benzonitrile at a platinum working electrode. Electrocatalysis at t
he film-coated electrode occurred for anions of n = 1 and 2 in 0.1 M (
TBA)PF6 in acetonitrile. For solution electrocatalysis, the second-ord
er catalytic rate constants were determined by voltammetry at a rotati
ng disk electrode under pseudo-first-order conditions with respect to
the alpha,omega-diiodoalkanes. The determined k values increase in the
order C-5 < C-8 < C-4 < C-3 < C-6 much less than C-2 for the number o
f carbon atoms of the alkyl chain of the alpha,omega-diiodoalkanes. Th
e GC-MS and HPLC product analyses of the constant potential bulk elect
rolyses revealed that alkanes, alkenes, and monoiodoalkyl derivatives
are formed primarily, except for the reaction of C-60(3-) with either
1,3-diiodopropane or 1,5-diiodopentane where formation of the C-60 add
ucts is favored.