Selective Decomposition of Cyclohexyl Hydroperoxide using Homogeneous and Heterogeneous CrVI Catalysts: Optimizing the Reaction by Evaluating the Reaction Mechanism,ChemCatChem

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Selective Decomposition of Cyclohexyl Hydroperoxide using Homogeneous and Heterogeneous CrVI Catalysts: Optimizing the Reaction by Evaluating the Reaction Mechanism
ChemCatChem ( IF 3.8 ) Pub Date : 2018-02-16 , DOI: 10.1002/cctc.201701909
Jessica Nadine Hamann ₁ , Marko Hermsen _{1,

2} , Anna-Corina Schmidt ₁ , Saskia Krieg ₃ , Jasmin Schießl ₄ , Dominic Riedel ₅ , Joaquim Henrique Teles ₅ , Ansgar Schäfer ₂ , Peter Comba ₃ , A. Stephen K. Hashmi _{1,

4} , Thomas Schaub _{1,

5}

Affiliation

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.

中文翻译：

均相和异相CrVI催化剂选择性分解氢过氧化环己基酯：通过评估反应机理优化反应

在这项研究中，就环己基氢过氧化物（CHHP）分解过程中有利于形成环己酮的问题，研究了已知的均相和异相铬（VI）催化剂体系。重点是使用不同的光谱学方法进行的机理研究以及DFT计算，以进一步优化反应条件。如先前的分解研究中所示，可能是通过形成烷基金属过氧化物中间体形成的机理。原位光谱研究表明，在可溶和不可溶催化剂的情况下，选择性分解都是通过Cr ^VI阶段的非自由基，非氧化还原机制通过形成环己基过氧铬（VI）络合物而发生的。详尽的DFT计算支持所提出的机制。

更新日期：2018-02-16

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