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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Bibliographic Details
Published in:ChemCatChem 2018-07, Vol.10 (13), p.2755-2767
Main Authors: Hamann, Jessica Nadine, Hermsen, Marko, Schmidt, Anna‐Corina, Krieg, Saskia, Schießl, Jasmin, Riedel, Dominic, Teles, Joaquim Henrique, Schäfer, Ansgar, Comba, Peter, Hashmi, A. Stephen K., Schaub, Thomas
Format: Article
Language:English
Subjects:
Catalysis
Catalysts
Chromium
cyclohexane oxidation
Cyclohexanone
cyclohexyl hydroperoxide
Decomposition
Decomposition reactions
homogeneous catalysis
kinetic
Mathematical analysis
Optimization
Reaction mechanisms
Spectroscopic analysis
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Summary: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. A look behind the scenes: Known homogeneous and heterogeneous CrVI systems were used to investigate the mechanism behind the transition metal‐catalyzed selective decomposition of cyclohexyl hydroperoxide. Based on comprehensive experimental as well as DFT studies, a non‐radical, non‐redox mechanism via a cyclohexylperoxychromium(VI) complex is proposed.
ISSN:1867-3880
1867-3899
DOI:10.1002/cctc.201701909