Molybdenum versus tungsten for the epoxidation of cyclooctene catalyzed by [Cp*2M2O5]

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dc.contributor.authorSözen-Aktaş P.
dc.contributor.authorManoury E.
dc.contributor.authorDemirhan F.
dc.contributor.authorPoli R.
dc.date.accessioned2024-07-22T08:19:04Z
dc.date.available2024-07-22T08:19:04Z
dc.date.issued2013
dc.description.abstractThe catalytic activity of [Cp*2M2O5] (M = Mo, W; Cp* = pentamethylcyclopentadienyl) for the homogeneous epoxidation of a solution of cyclooctene in MeCN/toluene follows the order Mo >> W when using tert-butyl hydroperoxide (TBHP)/decane as oxidant, in contrast to the inverse order (W >> Mo) when using aqueous H 2O2 as oxidant. The catalytic activity for the Mo system strongly depends on the solvent used to deliver the oxidant (TBHP/decane >> TBHP/H2O). The low activity of the W system is also decreased when using TBHP/water in place of TBHP/decane. For both metals, H 2O2/H2O is a better oxidant than TBHP/H 2O. However, whereas the Mo-based catalyst is much more active for the TBHP/decane epoxidation in spite of the lower TBHP oxidizing power (TBHP/decane > H2O2/H2O > TBHP/H 2O), the W-based system is much more active for the H 2O2/H2O epoxidation in spite of the negative effect of water (H2O2/H2O > TBHP/decane > TBHP/H2O). The kinetic profile of the TBHP/decane epoxidation process is affected by product inhibition. Initial rate measurements show that the rate law is first order with respect to substrate and has saturation behavior with respect to the oxidant. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
dc.identifier.DOI-ID10.1002/ejic.201300260
dc.identifier.issn14341948
dc.identifier.urihttp://akademikarsiv.cbu.edu.tr:4000/handle/123456789/17501
dc.language.isoEnglish
dc.publisherWiley-VCH Verlag
dc.rightsAll Open Access; Green Open Access
dc.subjectCatalysis
dc.subjectCatalyst activity
dc.subjectEpoxidation
dc.subjectMolybdenum
dc.subjectOxidants
dc.subjectCycloalkenes
dc.subjectCyclooctene
dc.subjectEffect of water
dc.subjectHomogeneous catalysis
dc.subjectKinetic profiles
dc.subjectMo-based catalysts
dc.subjectPentamethylcyclopentadienyl
dc.subjectPower
dc.subjectProduct inhibition
dc.subjectTert-butylhydroperoxide
dc.subjectTungsten
dc.titleMolybdenum versus tungsten for the epoxidation of cyclooctene catalyzed by [Cp*2M2O5]
dc.typeArticle

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