KINETICS AND MECHANISM OF THE OXIDATION OF IODIDE BY TRANS-DIOXORUTHENIUM(VI)

被引：10
|
作者：
LAU, TC
LAU, KWC
LAU, K
机构：
来源：
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1994年 / 21期
关键词：
D O I：
10.1039/dt9940003091
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The kinetics of reduction of trans-[Ru(tmc)O2]2+ (tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) by iodide has been studied in aqueous acidic solution. The reaction has the following stoichiometry: trans-[Ru(VI)(tmc)O2]2+ + 31- + 2H+ --> trans-[Ru(IV)(tmc)O(OH2)]2+ + l3-. The rate law is -d[Ru(VI)]/dt = (k(a) + k(b)]H+]) [Ru(VI)] [l-] with k(a) = 0.041 +/- 0.013 dm3 mol-1 s-1 and k(b) = 18.5 +/- 0.2 dm6 mol-2 s-2 at 25.0 degrees-C and 0.1 mol dm-3 ionic strength. For k(a) DELTAH(double dagger) = 42.9 +/- 9.4 kJ mol-1 and DELTAS(double dagger) = -131 +/- 40J K-1 mol-1, while for k(b), DELTAH(double dagger) = 36.9 +/- 2.9 kJ mol-1 and DELTAS(double dagger) = -97 +/- 10 J K-1 mol-1. A mechanism involving oxgen-atom transfer from Ru(VI) to iodide is consistent with the data.
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页码：3091 / 3093
页数：3
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