Comparative Study of Chromium(V) and Chromium(VI) Oxidation of Dialkyl Sulfides

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• 作者：Ganesan ; Tharumeya Kuppusamy ; Rajagopal ; Seenivasan ; Bharathy ; Jesuraja Bosco
• 关键词：Cr(V) and Cr(VI) ; oxidation of dialkyl sulfides ; kinetics and mechanism
• 刊名：Tetrahedron
• 出版年：2000
• 出版时间：August 4, 2000
• 年：2000
• 卷：56
• 期：32
• 页码：5885-5892
• 全文大小：140 K

文摘

The kinetics of the redox reaction of dialkyl sulfides, model compounds for methionine containing peptides, with Cr^V and Cr^VI has been studied spectrophotometrically in aqueous CH₃CN. Both reactions follow overall second-order kinetics, first order each in sulfide and oxidant. The rate of the reaction with Cr^V is two orders more than Cr^VI. Based on the substituent and solvent effect an outer-sphere electron transfer mechanism has been proposed for Cr^V oxidation. Two different mechanisms, one involving nucleophilic attack of sulfide on chromium and the other, an electron transfer from sulfide to Cr, has been proposed for the Cr^VI oxidation.