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The Oxygen Rebound Mechanism of C-H Bond Oxidation Reaction by Non-Heme Manganese-Oxygen Species

Title
The Oxygen Rebound Mechanism of C-H Bond Oxidation Reaction by Non-Heme Manganese-Oxygen Species
Authors
Lee, Yujeong
DGIST Authors
Lee, Yujeong; Cho, Jaeheung; Lee, Sunggi
Advisor(s)
조재흥
Co-Advisor(s)
Lee, Sunggi
Issue Date
2020
Available Date
2020-08-06
Degree Date
2020/08
Type
Thesis
Description
Manganese(IV)–hydroxo complex, C–H bond activation, Oxygen non-rebound mechanism
Abstract
A high-valent manganese–hydroxo complex has been synthesized and characterized using various physicochemical methods such as UV–vis, ESI-MS, IRPD, and DFT calculations. Generally, manganese-oxygen adducts can activate C–H bond through an oxygen non-rebound mechanism where the rate of hydrogen atom transfer (HAT) depends on the strength of C–H bond. Herein, in the formation process of manganese–hydroxo complex, [MnIV(CHDAP–O)(OH)]2+, the C–H bond activation of the 2,6 position in cyclohexyl groups unusally proceeds via an oxygen rebound mechanism, in which HAT is identified as a rate determining step.
Table Of Contents
Contents Abstract i List of contents iii List of figures iv List of tables vi I. Introduction II. Experimental section 2.1 Materials and Instrumentation 2 2.2 Synthesis 3 2.2.1 A deuterated CHDAP ligand 3 2.2.2 [MnII(CHDAP)(OTf)2] 5 2.2.3 [MnIV(CHDAP–O)(OH)]2+ 6 2.3 X-ray crystallography 6 III. Results and discussion 3.1 Preparation and Characterization of a Deuterated CHDAP Ligand 10 3.2 Synthesis and Characterization of a Manganese(II)-Starting Complex 12 3.3 Synthesis and Characterization of a Manganese(IV)–Hydroxo Complex 15 3.4 The Effect of the Deuterium Exchange in the 2,6 Position of Cyclohexyl Groups 20 3.5 Consideration 27 IV. Conclusion List of figures
URI
http://dgist.dcollection.net/common/orgView/200000321130
http://hdl.handle.net/20.500.11750/12179
DOI
https://doi.org/10.22677/thesis.200000321130
Degree
Master
Department
Department of Emerging Materials Science
University
DGIST
Related Researcher
  • Author Lee, Sunggi Organic Synthesis & Catalysis Lab
  • Research Interests Organic synthesis, Catalyst development, Reaction development, Radical chemistry, Stereoselective reaction
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Collection:
Department of Emerging Materials ScienceThesesMaster


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