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

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

doi:10.1016/0022-0728(87)80045-1

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

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

Research output: Journal article publication › Journal article › Academic research › peer-review

64 Citations (Scopus)

Abstract

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 language	English
Pages (from-to)	211-226
Number of pages	16
Journal	Journal of Electroanalytical Chemistry
Volume	226
Issue number	1-2
DOIs	https://doi.org/10.1016/0022-0728(87)80045-1
Publication status	Published - 10 Jul 1987
Externally published	Yes

ASJC Scopus subject areas

Analytical Chemistry
General Chemical Engineering
Electrochemistry

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10.1016/0022-0728(87)80045-1

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title = "Effects of electrode surface pretreatments on the electrochemistry of a macrocyclic dioxoruthenium(VI) complex",

abstract = "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.",

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AU - Che, Chi Ming

AU - Wong, Kwok Yin

AU - Anson, Fred C.

PY - 1987/7/10

Y1 - 1987/7/10

N2 - 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.

AB - 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.

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DO - 10.1016/0022-0728(87)80045-1

M3 - Journal article

SN - 0022-0728

VL - 226

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JO - Journal of Electroanalytical Chemistry

JF - Journal of Electroanalytical Chemistry

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

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