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Insights on the mechanistic features of catalytic oxidations of simple and conjugated olefins promoted by VO(acac)2/H2O2 system, in acetonitrile: A computational study

Paper ID Volume ID Publish Year Pages File Format Full-Text
55154 47042 2012 7 PDF Available
Title
Insights on the mechanistic features of catalytic oxidations of simple and conjugated olefins promoted by VO(acac)2/H2O2 system, in acetonitrile: A computational study
Abstract

A computational study based on standard Density Functional Theory and polarized continuum model has been carried out for investigating the essential mechanistic features occurring in the catalytic oxidation of two model substrates, namely ethylene and 1,3-butadiene, promoted by vanadyl acetylacetonate [VO(acac)2] in the presence of hydrogen peroxide. Results, showing in general a qualitative agreement with experimental data carried out on more complex systems, provide quite different scenarios depending on the conditions employed for the reaction. In particular, under thermodynamic control, no selectivity is observed between the two competitive routes, either epoxidation or double bond oxidative cleavage, in both the substrates. On the other hand, under kinetic control, in both systems the double bond oxidative cleavage is always the favored path, although in the case of 1,3-butadiene the difference with the epoxidation route is enhanced, this confirming that the selectivity is sensitive to the nature of the substituent in the vinyl position.

Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (103 K)Download as PowerPoint slideHighlights► A computational study, investigated the most important species present in the [VO(acac)2]/H2O2 mixture, in acetonitrile. ► No selectivity is observed, under thermodynamic control, between the two competitive routes, i.e. epoxidation and double bond oxidative cleavage. ► The oxidative cleavage is always the preferred path, under a kinetic control.

Keywords
Oxovanadium complex; Olefin catalytic oxidations; Hydrogen peroxide; Density Functional Theory; Reaction mechanisms
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Insights on the mechanistic features of catalytic oxidations of simple and conjugated olefins promoted by VO(acac)2/H2O2 system, in acetonitrile: A computational study
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Publisher
Database: Elsevier - ScienceDirect
Journal: Catalysis Today - Volume 192, Issue 1, 30 September 2012, Pages 56–62
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us