Molybdenum versus Tungsten for the Epoxidation of Cyclooctene Catalyzed by [Cp*2M2O5]

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dc.contributor.authorSözen-Aktas, P
dc.contributor.authorManoury, E
dc.contributor.authorDemirhan, F
dc.contributor.authorPoli, R
dc.date.accessioned2024-07-18T12:05:39Z
dc.date.available2024-07-18T12:05:39Z
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 H2O2 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, H2O2/H2O is a better oxidant than TBHP/H2O. 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/H2O), the W-based system is much more active for the H2O2/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.
dc.identifier.issn1434-1948
dc.identifier.urihttp://akademikarsiv.cbu.edu.tr:4000/handle/123456789/9902
dc.language.isoEnglish
dc.publisherWILEY-V C H VERLAG GMBH
dc.subjectOLEFIN EPOXIDATION
dc.subjectETA(5)-CYCLOPENTADIENYL MOLYBDENUM
dc.subjectHYDROGEN-PEROXIDE
dc.subjectALKYL HYDROPEROXIDES
dc.subjectTRICARBONYL COMPLEX
dc.subjectGREEN EPOXIDATION
dc.subjectORGANIC-SOLVENT
dc.subjectIONIC LIQUIDS
dc.subjectPRECURSORS
dc.subjectMECHANISM
dc.titleMolybdenum versus Tungsten for the Epoxidation of Cyclooctene Catalyzed by [Cp*2M2O5]
dc.typeArticle

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