Kinetics and mechanism of the oxidation of alkenes and silanes by hydrogen peroxide catalyzed by methylrhenium trioxide (MTO) and a novel application of electrospray mass spectrometry to study the hydrolysis of MTO

dc.contributor.advisor James H. Espenson
dc.contributor.advisor Robert S. Houk
dc.contributor.author Tan, Haisong
dc.contributor.department Chemistry
dc.date 2018-08-23T02:20:44.000
dc.date.accessioned 2020-06-30T07:18:52Z
dc.date.available 2020-06-30T07:18:52Z
dc.date.copyright Fri Jan 01 00:00:00 UTC 1999
dc.date.issued 1999
dc.description.abstract <p>Conjugated dienes were oxidized by hydrogen peroxide with methylrhenium trioxide as catalyst. As is true for other MTO-catalyzed reactions, methylrhenium bis-peroxide (CH3Re(O)(eta2-O2)2(H 2O)) was the major reactive catalyst present. The rate constants between it and the dienes, increase or decrease as substituents add or remove electron density from the double bond, suggesting a concerted mechanism in which the peroxide oxygen attacks the double bond electrophilically. The H2O 2/MTO oxidation system was also used in the regioselective cyclization of hydroxyalkenes to tetrahydrofurans and unsaturated carboxylic acids to lactones. In these reactions MTO acts as a bifunctional catalyst for both epoxidation and cyclization reactions. The reactions of trisubstituted silane with hydrogen peroxide catalyzed by MTO result in its quantitative convertion to silanol. An oxene mechanism is proposed for this reaction based on the kinetics and isotope ratio study;The full kinetics pH profile for the base-promoted decomposition of MTO to CH4 and ReO4-- was examined with the inclusion of new data at pH 7--10. Spectroscopic and kinetics data gave evidence for mono-and dihydroxo complexes: MTO(OH--) and MTO(OH--)2. Some kinetic data were acquired with electrospray mass spectrometry to monitor the build up in the concentration of perrhenate ions.</p>
dc.format.mimetype application/pdf
dc.identifier archive/lib.dr.iastate.edu/rtd/12172/
dc.identifier.articleid 13171
dc.identifier.contextkey 6766912
dc.identifier.doi https://doi.org/10.31274/rtd-180813-13449
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath rtd/12172
dc.identifier.uri https://dr.lib.iastate.edu/handle/20.500.12876/65511
dc.language.iso en
dc.source.bitstream archive/lib.dr.iastate.edu/rtd/12172/r_9940244.pdf|||Fri Jan 14 19:14:33 UTC 2022
dc.subject.disciplines Analytical Chemistry
dc.subject.disciplines Inorganic Chemistry
dc.subject.keywords Chemistry
dc.subject.keywords Inorganic chemistry
dc.subject.keywords Analytical chemistry
dc.title Kinetics and mechanism of the oxidation of alkenes and silanes by hydrogen peroxide catalyzed by methylrhenium trioxide (MTO) and a novel application of electrospray mass spectrometry to study the hydrolysis of MTO
dc.type article
dc.type.genre dissertation
dspace.entity.type Publication
relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
thesis.degree.level dissertation
thesis.degree.name Doctor of Philosophy
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