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Selective decomposition of cyclohexyl hydroperoxide using homogeneous and heterogeneous CrVI catalysts: optimizing the reaction by evaluating the reaction mechanism

In this study, known homogeneous and heterogeneous chromium(VI) catalyst systems were investigated with respect to the favored formation of cyclohexanone during the decomposition of cyclohexyl hydroperoxide (CHHP). The focus was on mechanistic studies using different spectroscopic methods as well as...

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Hauptverfasser: Hamann, Jessica Nadine (VerfasserIn) , Hermsen, Marko (VerfasserIn) , Schmidt, Anna-Corina (VerfasserIn) , Krieg, Saskia (VerfasserIn) , Schießl, Jasmin (VerfasserIn) , Comba, Peter (VerfasserIn) , Hashmi, A. Stephen K. (VerfasserIn) , Schaub, Thomas (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 11 January 2018
In: ChemCatChem
Year: 2018, Jahrgang: 10, Heft: 13, Pages: 2755-2767
ISSN:1867-3899
DOI:10.1002/cctc.201701909
Online-Zugang:Verlag, Volltext: http://dx.doi.org/10.1002/cctc.201701909
Verlag, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/cctc.201701909
Volltext
Verfasserangaben:Jessica Nadine Hamann, Marko Hermsen, Anna-Corina Schmidt, Saskia Krieg, Jasmin Schießl, Dominic Riedel, Joaquim Henrique Teles, Ansgar Schäfer, Peter Comba, A. Stephen K. Hashmi, Thomas Schaub
Beschreibung
Zusammenfassung:In this study, known homogeneous and heterogeneous chromium(VI) catalyst systems were investigated with respect to the favored formation of cyclohexanone during the decomposition of cyclohexyl hydroperoxide (CHHP). The focus was on mechanistic studies using different spectroscopic methods as well as DFT calculations to further optimize the reaction conditions. As in previous decomposition studies, a mechanism via the formation of a metal alkylperoxido intermediate is probable. In situ spectroscopic studies revealed that in case of both the soluble and insoluble catalyst, the selective decomposition happens via a non-radical, non-redox mechanism at the CrVI stage through the formation of a cyclohexylperoxychromium(VI) complex. The proposed mechanism is supported by thorough DFT calculations.
Beschreibung:Gesehen am 29.08.2018
Beschreibung:Online Resource
ISSN:1867-3899
DOI:10.1002/cctc.201701909

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