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Selective Decomposition of Cyclohexyl Hydroperoxide using Homogeneous and Heterogeneous Cr VI Catalysts: Optimizing the Reaction by Evaluating the Reaction Mechanism
Author(s) -
Hamann Jessica Nadine,
Hermsen Marko,
Schmidt AnnaCorina,
Krieg Saskia,
Schießl Jasmin,
Riedel Dominic,
Teles Joaquim Henrique,
Schäfer Ansgar,
Comba Peter,
Hashmi A. Stephen K.,
Schaub Thomas
Publication year - 2018
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201701909
Subject(s) - catalysis , decomposition , chemistry , cyclohexanone , reaction mechanism , chromium , homogeneous catalysis , redox , homogeneous , heterogeneous catalysis , photochemistry , computational chemistry , inorganic chemistry , organic chemistry , thermodynamics , physics
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 Cr VI stage through the formation of a cyclohexylperoxychromium(VI) complex. The proposed mechanism is supported by thorough DFT calculations.