Abstract
The oxidation of
cyclohexanol by ferricyanide in alkaline aqueous solution is catalysed by micromolar
concentrations of K3RuCl6. The rate law at 25.0�C in pH
11.9 phosphate buffer containing 0.50 M NaCl is -d[FeIII]/dt = [Ru](2klk2[alcohol][FeIII])/(2kl[alcohol] + k2[FeIII])
with kl 12 � 2 mol-1 1. s-1 and k2 (2.5 � 0.2) × 102 mol-1
1. s-1. A deuterium isotope effect
of about 4 is observed when (D12)cyclohexanol is used. A mechanism
consistent with these observations involves reduction of the RuIII
catalyst by hydride transfer from the alcohol followed by reoxidation by
ferricyanide to the original RulIII state.
Cited by
9 articles.
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