Oxidation of organic sulfides by electrophilically-activated hydrogen peroxide: The catalytic ability of methylrhenium trioxide

Journal Article · Wed Nov 23 04:00:00 EST 1994 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic00102a023· OSTI ID:47957

Vassell, K A; Espenson, J H ^[1]

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1. Iowa State Univ., Ames, IA (United States)

A family of organic sulfides was oxidized to the corresponding sulfoxides by hydrogen peroxide. Such reactions are, however, very slow and meaningless in practice without an effective catalyst. The oxidation was successfully catalyzed by CH{sub 3}ReO{sub 3}, a water-soluble organometallic oxide. A kinetic study was carried out in 1:1 (v/v) acetonitrile-water at pH 1 and at 25{degrees}C. The kinetics can be resolved into two steps. First, H{sub 2}O{sub 2} and CH{sub 3}ReO{sub 3} react to form 1:1 and 2:1 rhenium peroxides, denoted as A and B, respectively. In the second step A and B react with the substrate forming the product. The rate constants for the various steps of these reactions were evaluated using steady-state techniques and are on the order of 10{sup 3} L mol{sup {minus}1} s{sup {minus}1} for aryl methyl sulfides and 10{sup 4} L mol{sup {minus}1} s{sup {minus}1} for dialkyl sulfides. Both A and B are reactive, A moreso than B. The kinetic results point to a mechanism that involves the nucleophilic attack of the sulfur atom on a peroxide oxygen of the rhenium peroxides. This formulation is consistent with the accelerating effects of electron-donating substituents.

• Sponsoring Organization: USDOE
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 47957
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 24 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
40 CHEMISTRY
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
HYDROGEN PEROXIDE
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
RHENIUM COMPOUNDS