Epoxidation of olefins by H2O2 as catalyzed by methylrhenium trioxide, CH3ReO3, was investigated in semi-aqueous and organic solvents. Methylrhenium oxide activates H2O2 through formation of a mono-peroxo-Re(VII), A, and a bisperoxo-Re(VII), B, species. Both species are active toward olefin epoxidation with very similar reactivities and are about 105 times more reactive than free H2O2. Epoxides, the initial products from these reactions, undergo ring-opening to the 1,2-diols. A concerted mechanism that involves external nucleophilic attack of the olefin on the peroxy oxygen has been proposed;The kinetics and the mechanisms of oxidations of 1,2-diols, phenols and H2O2 by the pentaaquaoxochromium(IV) ion, CrO2+ were studied in aqueous acidic solutions. Oxidation of vicinal diols with CrO2+ involves a hydride abstraction from the [alpha]-position (primary and secondary 1,2-diols) or from the [beta]-position (pinacol). Reactions of phenols with CrO2+ produce the corresponding phenoxyl radicals in a rate-determining-step. The phenoxyl radicals are further oxidized by the superoxochromiun(III), CrOO2+, to produce quinones as final products. Oxidation of H2O2 with CrO2+ produces CrOO2+ in the presence and in the absence of O2.
","abstract_html":"<p>Epoxidation of olefins by H2O2 as catalyzed by methylrhenium trioxide, CH3ReO3, was investigated in semi-aqueous and organic solvents. Methylrhenium oxide activates H2O2 through formation of a mono-peroxo-Re(VII), A, and a bisperoxo-Re(VII), B, species. Both species are active toward olefin epoxidation with very similar reactivities and are about 105 times more reactive than free H2O2. Epoxides, the initial products from these reactions, undergo ring-opening to the 1,2-diols. A concerted mechanism that involves external nucleophilic attack of the olefin on the peroxy oxygen has been proposed;The kinetics and the mechanisms of oxidations of 1,2-diols, phenols and H2O2 by the pentaaquaoxochromium(IV) ion, CrO2+ were studied in aqueous acidic solutions. Oxidation of vicinal diols with CrO2+ involves a hydride abstraction from the [alpha]-position (primary and secondary 1,2-diols) or from the [beta]-position (pinacol). Reactions of phenols with CrO2+ produce the corresponding phenoxyl radicals in a rate-determining-step. The phenoxyl radicals are further oxidized by the superoxochromiun(III), CrOO2+, to produce quinones as final products. Oxidation of H2O2 with CrO2+ produces CrOO2+ in the presence and in the absence of O2.</p>","abstract_has_math":false,"creators":["Al-Ajlouni, Ahmad"],"institution":null,"degree_name":"Doctor of Philosophy","degree_level":"dissertation","degree_discipline":null,"degree_department":"Department of Chemistry","school":null,"contributors":[],"advisors":["James H. Espenson"],"committee_chairs":[],"committee_members":[],"year":1995,"date_issued":"1995","date_published":"1995","updated_at":"2026-07-24T02:39:41Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier.doi","label":"DOI","values":["https://doi.org/10.31274/rtd-180813-11418"],"render_values":[{"text":"https://doi.org/10.31274/rtd-180813-11418","href":"https://doi.org/10.31274/rtd-180813-11418","code":true}]},{"key":"dc:identifier","label":"Identifier","values":["archive/lib.dr.iastate.edu/rtd/10998/"],"render_values":[{"text":"archive/lib.dr.iastate.edu/rtd/10998/","href":null,"code":true}]}]},"links":{"outbound_url":"https://dr.lib.iastate.edu/handle/20.500.12876/64205","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["James H. 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Methylrhenium oxide activates H2O2 through formation of a mono-peroxo-Re(VII), A, and a bisperoxo-Re(VII), B, species. Both species are active toward olefin epoxidation with very similar reactivities and are about 105 times more reactive than free H2O2. Epoxides, the initial products from these reactions, undergo ring-opening to the 1,2-diols. A concerted mechanism that involves external nucleophilic attack of the olefin on the peroxy oxygen has been proposed;The kinetics and the mechanisms of oxidations of 1,2-diols, phenols and H2O2 by the pentaaquaoxochromium(IV) ion, CrO2+ were studied in aqueous acidic solutions. Oxidation of vicinal diols with CrO2+ involves a hydride abstraction from the [alpha]-position (primary and secondary 1,2-diols) or from the [beta]-position (pinacol). Reactions of phenols with CrO2+ produce the corresponding phenoxyl radicals in a rate-determining-step. The phenoxyl radicals are further oxidized by the superoxochromiun(III), CrOO2+, to produce quinones as final products. Oxidation of H2O2 with CrO2+ produces CrOO2+ in the presence and in the absence of O2.
"]},{"key":"dc:format.mimetype","label":"Dc Format Mimetype","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Kinetics and mechanisms of oxidation of organic and inorganic substrates by transition metal oxo complexes"]}]}],"canonical_facts":{"dc:contributor.advisor":["James H. Espenson"],"dc:contributor.department":["Department of Chemistry"],"dc:creator":["Al-Ajlouni, Ahmad"],"dc:date":["2018-08-23T04:28:34.000"],"dc:date.accessioned":["2020-06-30T07:09:20Z"],"dc:date.available":["2020-06-30T07:09:20Z"],"dc:date.issued":["1995"],"dc:description.abstract":["Epoxidation of olefins by H2O2 as catalyzed by methylrhenium trioxide, CH3ReO3, was investigated in semi-aqueous and organic solvents. Methylrhenium oxide activates H2O2 through formation of a mono-peroxo-Re(VII), A, and a bisperoxo-Re(VII), B, species. Both species are active toward olefin epoxidation with very similar reactivities and are about 105 times more reactive than free H2O2. Epoxides, the initial products from these reactions, undergo ring-opening to the 1,2-diols. A concerted mechanism that involves external nucleophilic attack of the olefin on the peroxy oxygen has been proposed;The kinetics and the mechanisms of oxidations of 1,2-diols, phenols and H2O2 by the pentaaquaoxochromium(IV) ion, CrO2+ were studied in aqueous acidic solutions. Oxidation of vicinal diols with CrO2+ involves a hydride abstraction from the [alpha]-position (primary and secondary 1,2-diols) or from the [beta]-position (pinacol). Reactions of phenols with CrO2+ produce the corresponding phenoxyl radicals in a rate-determining-step. The phenoxyl radicals are further oxidized by the superoxochromiun(III), CrOO2+, to produce quinones as final products. Oxidation of H2O2 with CrO2+ produces CrOO2+ in the presence and in the absence of O2.
"],"dc:format.mimetype":["application/pdf"],"dc:identifier":["archive/lib.dr.iastate.edu/rtd/10998/"],"dc:identifier.doi":["https://doi.org/10.31274/rtd-180813-11418"],"dc:identifier.uri":["https://dr.lib.iastate.edu/handle/20.500.12876/64205"],"dc:language.iso":["en"],"dc:title":["Kinetics and mechanisms of oxidation of organic and inorganic substrates by transition metal oxo complexes"],"dc:type":["dissertation"],"thesis:degree_level":["dissertation"],"thesis:degree_name":["Doctor of Philosophy"]},"updated_at":"2026-07-24T02:39:41Z"}