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

被引：9
作者：
Lau, TC
Chow, KH
Lau, KWC
Tsang, WYK
机构：
[1] Department of Biology and Chemistry, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong
来源：
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1997年 / 03期
关键词：
D O I：
10.1039/a603655d
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The kinetics of the oxidation of SO32- by trans-[Ru(tmc)O-2](2+) (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been studied in aqueous solution at 25.0 degrees C. The reaction had the following stoichiometry: trans-[Ru-VI(tmc)O-2](2+) + SO32- + H2O --> trans-[Ru-IV(tmc)O(OH2)](2+) + SO42-. Sulfite and sulfur-containing products were analysed by ion chromatography. No S2O62- 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) x 10(4) dm(3) mol(-1) s(-1) and K = (3.4 +/- 1.0) x 10(-7) mol dm(-3) at I = 1.0 mel 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.
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页码：313 / 315
页数：3
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