Spectral and mechanistic investigations of ruthenium(III) catalyzed oxidation of atenolol by diperiodatocuprate(III) in aqueous alkaline medium

被引:1
|
作者
Patil, R. K. [1 ]
Nandibewoor, S. T. [1 ]
Chimatadar, S. A. [1 ]
机构
[1] Karnatak Univ, PK Dept Studies Chem, Dharwad 580003, Karnataka, India
关键词
atenolol; diperiodatocuprate(III); ruthenium(III); kinetics; KINETICS; WATER; ACID;
D O I
10.1134/S0036024412030247
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The kinetics of ruthenium(III) catalyzed oxidation of atenolol by diperiodatocuprate(III) in aqueous alkaline medium at a constant ionic strength of I = 0.10 M has been studied spectrophotometrically at 27A degrees C. The reaction between diperiodatocuprate(III) and atenolol in alkaline medium in presence of ruthenium(III) exhibits 2: 1 stoichiometry (atenolol: diperiodatocuprate(III)). The main products were identified by spot test, IR, NMR, and LC-MS. The reaction is of first order in DPC concentrations and has less than unit order in both ATN and alkali concentrations. The order in ruthenium(III) was unity. Intervention of free radicals was observed in the reaction. Increase in periodate concentration decreases the rate. The oxidation reaction in alkaline medium has been shown to proceed via a ruthenium(III)-atenolol complex, which reacts with monoperiodatocuprate(III) in a rate determining step followed by other fast steps to give the products. Probable mechanism is proposed and discussed. The activation parameters with respect to the slow step of the mechanism and thermodynamic quantities were determined and discussed.
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页码:369 / 374
页数:6
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