skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Oxidation of sulfoxides by hydrogen peroxide, catalyzed by methyltrioxorhenium(VII)

Abstract

Dialkyl and diaryl sulfoxides are oxidized to sulfones by hydrogen peroxide using methyltrioxorhenium as the catalyst. The reaction rate is negligible without a catalyst. The kinetics study was performed in CH{sub 3}CN-H{sub 2}O (4:1 v/v) at 298 K with [H{sup +}] at 0.1 M, conditions which make the equilibration between MTO and its peroxo complexes more rapid than the oxygen-transfer step. The values for the rate constant for the oxygen-transfer step lie in the range 0.1--3 L mol{sup {minus}1} s{sup {minus}1}. The rate constants were significantly smaller than for the oxidation of sulfides to sulfoxides. A study of ring-substituted diaryl sulfoxides yielded kinetics results that are consistent with nucleophilic attack of the sulfur atom on the peroxide oxygen group since {rho} = {minus}0.65. The results cited refer to the reactions of the diperoxo from the catalyst, MeRe(O)({eta}{sup 2}-O{sub 2}){sub 2}H{sub 2}O. The monoperoxo complex showed no measurable reactivity toward sulfoxides, in contrast with the situation for nearly every other substrate. That unusual finding suggests a hydrogen-bonded interaction between the substrate and the diperoxorhenium compound which cannot exist with the monoperoxo compound.

Authors:
;
Publication Date:
Research Org.:
Ames Lab., IA (US); Iowa State Univ. of Science and Technology, Ames, IA (US)
OSTI Identifier:
20075876
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 10; Other Information: PBD: 15 May 2000; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; OXIDATION; SULFOXIDES; HYDROGEN PEROXIDE; CATALYSIS; METHYL RADICALS; RHENIUM OXIDES; COMPLEXES; CHEMICAL REACTION KINETICS

Citation Formats

Lahti, D.W., and Espenson, J.H. Oxidation of sulfoxides by hydrogen peroxide, catalyzed by methyltrioxorhenium(VII). United States: N. p., 2000. Web. doi:10.1021/ic991292b.
Lahti, D.W., & Espenson, J.H. Oxidation of sulfoxides by hydrogen peroxide, catalyzed by methyltrioxorhenium(VII). United States. doi:10.1021/ic991292b.
Lahti, D.W., and Espenson, J.H. Mon . "Oxidation of sulfoxides by hydrogen peroxide, catalyzed by methyltrioxorhenium(VII)". United States. doi:10.1021/ic991292b.
@article{osti_20075876,
title = {Oxidation of sulfoxides by hydrogen peroxide, catalyzed by methyltrioxorhenium(VII)},
author = {Lahti, D.W. and Espenson, J.H.},
abstractNote = {Dialkyl and diaryl sulfoxides are oxidized to sulfones by hydrogen peroxide using methyltrioxorhenium as the catalyst. The reaction rate is negligible without a catalyst. The kinetics study was performed in CH{sub 3}CN-H{sub 2}O (4:1 v/v) at 298 K with [H{sup +}] at 0.1 M, conditions which make the equilibration between MTO and its peroxo complexes more rapid than the oxygen-transfer step. The values for the rate constant for the oxygen-transfer step lie in the range 0.1--3 L mol{sup {minus}1} s{sup {minus}1}. The rate constants were significantly smaller than for the oxidation of sulfides to sulfoxides. A study of ring-substituted diaryl sulfoxides yielded kinetics results that are consistent with nucleophilic attack of the sulfur atom on the peroxide oxygen group since {rho} = {minus}0.65. The results cited refer to the reactions of the diperoxo from the catalyst, MeRe(O)({eta}{sup 2}-O{sub 2}){sub 2}H{sub 2}O. The monoperoxo complex showed no measurable reactivity toward sulfoxides, in contrast with the situation for nearly every other substrate. That unusual finding suggests a hydrogen-bonded interaction between the substrate and the diperoxorhenium compound which cannot exist with the monoperoxo compound.},
doi = {10.1021/ic991292b},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 10,
volume = 39,
place = {United States},
year = {2000},
month = {5}
}