Kinetics and mechanism of the oxidation of sulfite by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)

Tai-Chu Lau; Kwok-Ho Chow; Kent W. C. Lau; Wenny Y. K. Tsang

Kinetics and mechanism of the oxidation of sulfite by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)

Tai-Chu Lau
, Kwok-Ho Chow
, Kent W. C. Lau
, Wenny Y. K. Tsang

Research output: Journal Publications and Reviews › RGC 22 - Publication in policy or professional journal

Abstract

The kinetics of the oxidation of SO₃ ^2- by trans-[Ru(tmc)O₂]²⁺ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been studied in aqueous solution at 25.0°C. The reaction has the following stoichiometry: trans-[Ru^VI(tmc)O₂]²⁺ + SO₃ ^2- + H₂O → trans-[Ru^IV(tmc)O(OH₂)]²⁺ + SO₄ ^2-. Sulfite and sulfur-containing products were analysed by ion chromatography. No S₂O₆ ^2- could be detected. The rate law is -d[Ru^VI]/dt = k/{1 + ([H⁺]/K)}[Ru^VI][S^IV] with k = (7.0 ± 1.4) × 10⁴ dm³ mol^-1 s^-1 and K= (3.4 ± 1.0) × 10^-7 mol dm^-3 at I = 1.0 mol dm^-3. The value of k is more than two orders of magnitude greater than predicted by Marcus theory, and an inner-sphere mechanism involving the intermediate [O=Ru^VI=O-SO₃] is proposed. This may decompose by one- or two-electron pathways.

Original language	English
Pages (from-to)	313-315
Journal	Journal of the Chemical Society - Dalton Transactions
Issue number	3
Publication status	Published - 7 Feb 1997

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@article{896cd9eaf6bb4d93b1ee5193c9ae2b09,

title = "Kinetics and mechanism of the oxidation of sulfite by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)",

abstract = "The kinetics of the oxidation of SO3 2- by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been studied in aqueous solution at 25.0°C. The reaction has the following stoichiometry: trans-[RuVI(tmc)O2]2+ + SO3 2- + H2O → trans-[RuIV(tmc)O(OH2)]2+ + SO4 2-. Sulfite and sulfur-containing products were analysed by ion chromatography. No S2O6 2- could be detected. The rate law is -d[RuVI]/dt = k/\{1 + ([H+]/K)\}[RuVI][SIV] with k = (7.0 ± 1.4) × 104 dm3 mol-1 s-1 and K= (3.4 ± 1.0) × 10-7 mol dm-3 at I = 1.0 mol dm-3. The value of k is more than two orders of magnitude greater than predicted by Marcus theory, and an inner-sphere mechanism involving the intermediate [O=RuVI=O-SO3] is proposed. This may decompose by one- or two-electron pathways.",

author = "Tai-Chu Lau and Kwok-Ho Chow and Lau, \{Kent W. C.\} and Tsang, \{Wenny Y. K.\}",

year = "1997",

month = feb,

day = "7",

language = "English",

pages = "313--315",

journal = "Journal of the Chemical Society - Dalton Transactions",

issn = "0300-9246",

publisher = "Royal Society of Chemistry",

number = "3",

}

Kinetics and mechanism of the oxidation of sulfite by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). / Lau, Tai-Chu; Chow, Kwok-Ho; Lau, Kent W. C. et al.
In: Journal of the Chemical Society - Dalton Transactions, No. 3, 07.02.1997, p. 313-315.

Research output: Journal Publications and Reviews › RGC 22 - Publication in policy or professional journal

TY - JOUR

T1 - Kinetics and mechanism of the oxidation of sulfite by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)

AU - Lau, Tai-Chu

AU - Chow, Kwok-Ho

AU - Lau, Kent W. C.

AU - Tsang, Wenny Y. K.

PY - 1997/2/7

Y1 - 1997/2/7

N2 - The kinetics of the oxidation of SO3 2- by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been studied in aqueous solution at 25.0°C. The reaction has the following stoichiometry: trans-[RuVI(tmc)O2]2+ + SO3 2- + H2O → trans-[RuIV(tmc)O(OH2)]2+ + SO4 2-. Sulfite and sulfur-containing products were analysed by ion chromatography. No S2O6 2- could be detected. The rate law is -d[RuVI]/dt = k/{1 + ([H+]/K)}[RuVI][SIV] with k = (7.0 ± 1.4) × 104 dm3 mol-1 s-1 and K= (3.4 ± 1.0) × 10-7 mol dm-3 at I = 1.0 mol dm-3. The value of k is more than two orders of magnitude greater than predicted by Marcus theory, and an inner-sphere mechanism involving the intermediate [O=RuVI=O-SO3] is proposed. This may decompose by one- or two-electron pathways.

AB - The kinetics of the oxidation of SO3 2- by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been studied in aqueous solution at 25.0°C. The reaction has the following stoichiometry: trans-[RuVI(tmc)O2]2+ + SO3 2- + H2O → trans-[RuIV(tmc)O(OH2)]2+ + SO4 2-. Sulfite and sulfur-containing products were analysed by ion chromatography. No S2O6 2- could be detected. The rate law is -d[RuVI]/dt = k/{1 + ([H+]/K)}[RuVI][SIV] with k = (7.0 ± 1.4) × 104 dm3 mol-1 s-1 and K= (3.4 ± 1.0) × 10-7 mol dm-3 at I = 1.0 mol dm-3. The value of k is more than two orders of magnitude greater than predicted by Marcus theory, and an inner-sphere mechanism involving the intermediate [O=RuVI=O-SO3] is proposed. This may decompose by one- or two-electron pathways.

UR - https://www.scopus.com/pages/publications/33748601594

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-33748601594&origin=recordpage

M3 - RGC 22 - Publication in policy or professional journal

SN - 0300-9246

SP - 313

EP - 315

JO - Journal of the Chemical Society - Dalton Transactions

JF - Journal of the Chemical Society - Dalton Transactions

IS - 3

ER -

Kinetics and mechanism of the oxidation of sulfite by trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)

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