Effects of electrode surface pretreatments on the electrochemistry of a macrocyclic dioxoruthenium(VI) complex

Chi Ming Che, Kwok Yin Wong, Fred C. Anson

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The reductive electrochemistry of trans-[RuVI(TMC)(O)2]2+(TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) follows different courses in aprotic and aqueous media. In acetonitrile, a one-electron reduction to trans-[RuV(TMC)(O)2]+occurs. In aqueous acid trans-[RuIV(TMC)O(OH2)]2+is formed in a single, two-electron, two-proton step. [RuV(TMC)(O)2]+disproportionates to [RuVI(TMC)(O)2]2+and [RuIV(TMC)O(OH2)]2+in the presence of acid. The oxidation of [RuIV(TMC)O(OH2)]2+in aqueous acid is facile at pyrolytic graphite and oxidatively "activated" glassy carbon electrodes but hindered at unactivated glassy carbon, platinum and gold electrodes. Slow proton transfer is identified as the origin of the slow oxidation and oxygen-containing groups on "activated" electrodes are suggested as the catalysts for this step.
Original languageEnglish
Pages (from-to)211-226
Number of pages16
JournalJournal of Electroanalytical Chemistry
Issue number1-2
Publication statusPublished - 10 Jul 1987
Externally publishedYes

ASJC Scopus subject areas

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

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